Seven hexamethylenetetramine (HMTA) complexes with mono- and dicarboxylic acids: analysis of packing modes of HMTA complexes in the literature

The crystal structures of seven hexamethylenetetramine (HMTA) complexes, or co-crystals, with carboxylic acid donor molecules are reported to explain the link between the molecular structure of HMTA and the crystal structure of the co-crystals, i.e. the dimension and shape of their hydrogen-bonded assembly. A comprehensive and detailed literature survey of HMTA complexes (38), be they neutral co-crystals or salts, with molecules containing carboxylic acid and phenol functional groups reveals that in general two N acceptors are used for strong O—H...N interactions. Owing to the relative arrangement of two of the four N atoms, the most common type of assembly features one-dimensional zigzag chains. Weak interactions of the C—H...N type are formed by N atoms not involved in strong interactions. These chains also form the basis of two-dimensional assemblies. These one- and two-dimensional assemblies feature either two or three functional groups. If only one functional group is on the donor molecule, then wing or V-shaped zero-dimensional assemblies are formed, which can be considered to be the building blocks for one- and two-dimensional assemblies. In general, the HMTA molecules form two-dimensional layers which are stabilized by weak hydrogen bonds. Co-crystals with cyclohexylcarboxylic acid (I), 4-fluorobenzoic acid (II), 4-methylbenzoic acid (III) and cinnamic acid (IV) all feature the V-shaped zero-dimensional assemblies. Co-crystals with cis-1,4-cyclohexyldicarboxylic acid (VI) and trans-1,4-cyclohexylcarboxylic acid (VII) feature the zigzag chains and can be structurally derived from co-crystal (I). Co-crystal (V), with 4-nitrobenzoic acid, has solvent water included and features hydrogen bonding to all four N atoms of the HMTA molecule.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2002).

Figures

(1) bis(cyclohexanecarboxylic acid)(hexamethylenetetramine)

Crystal data

C6H12N4·2(C7H12O2)	F(000) = 864
Mr = 396.53	Dx = 1.24 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2855 reflections
a = 6.0341 (1) Å	θ = 2.2–26.6°
b = 30.9087 (5) Å	µ = 0.09 mm^−1
c = 11.7024 (2) Å	T = 173 K
β = 103.366 (1)°	Plate, colourless
V = 2123.45 (6) Å^3	0.45 × 0.4 × 0.06 mm
Z = 4

Data collection

Bruker APEX II CCD area detector diffractometer	3862 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 28°, θmin = 2.2°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −7→7
Tmin = 0.96, Tmax = 0.99	k = −40→40
37573 measured reflections	l = −15→15
5102 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0631P)^2 + 0.7469P] where P = (Fo^2 + 2Fc^2)/3
5102 reflections	(Δ/σ)max = 0.001
259 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5685 (3)	0.25400 (5)	0.41806 (12)	0.0288 (3)
H1A	0.4834	0.2572	0.3354	0.035*
H1B	0.73	0.2483	0.4183	0.035*
C2	0.6793 (3)	0.28867 (5)	0.60562 (13)	0.0326 (3)
H2A	0.842	0.2834	0.6076	0.039*
H2B	0.6693	0.3155	0.6502	0.039*
C3	0.6056 (3)	0.21341 (5)	0.59490 (14)	0.0340 (3)
H3A	0.5461	0.1887	0.6325	0.041*
H3B	0.7674	0.2075	0.5963	0.041*
C4	0.2359 (2)	0.22641 (5)	0.47212 (13)	0.0304 (3)
H4A	0.1463	0.2292	0.3902	0.036*
H4B	0.1726	0.2019	0.5088	0.036*
C5	0.3091 (3)	0.30164 (5)	0.48156 (15)	0.0356 (4)
H5A	0.2941	0.3288	0.5241	0.043*
H5B	0.2211	0.305	0.3995	0.043*
C6	0.3487 (3)	0.26110 (6)	0.65710 (13)	0.0340 (3)
H6A	0.2859	0.2369	0.6951	0.041*
H6B	0.3354	0.2878	0.7018	0.041*
N1	0.4757 (2)	0.21717 (4)	0.47170 (10)	0.0273 (3)
N2	0.5522 (2)	0.29456 (4)	0.48213 (11)	0.0286 (3)
N3	0.5906 (2)	0.25266 (4)	0.66186 (10)	0.0315 (3)
N4	0.2141 (2)	0.26603 (4)	0.53624 (11)	0.0312 (3)
C7	0.7056 (3)	0.09253 (5)	0.28071 (13)	0.0296 (3)
H7	0.653	0.0693	0.3277	0.036*
C8	0.5546 (3)	0.09142 (5)	0.15629 (14)	0.0332 (3)
H8A	0.3935	0.0952	0.1599	0.04*
H8B	0.5961	0.1157	0.1102	0.04*
C9	0.5805 (3)	0.04894 (6)	0.09489 (16)	0.0437 (4)
H9A	0.5185	0.0251	0.1346	0.052*
H9B	0.491	0.0503	0.0126	0.052*
C10	0.8279 (3)	0.03941 (6)	0.09583 (17)	0.0483 (5)
H10A	0.839	0.0105	0.0611	0.058*
H10B	0.884	0.0611	0.047	0.058*
C11	0.9758 (3)	0.04050 (6)	0.21927 (18)	0.0473 (4)
H11A	1.137	0.0361	0.2165	0.057*
H11B	0.9312	0.0166	0.2657	0.057*
C12	0.9521 (3)	0.08354 (6)	0.27897 (16)	0.0423 (4)
H12A	1.0456	0.0829	0.3605	0.051*
H12B	1.01	0.1071	0.2366	0.051*
C13	0.6829 (3)	0.13555 (5)	0.33841 (13)	0.0307 (3)
O1	0.4867 (2)	0.14133 (4)	0.36419 (13)	0.0526 (4)
H1	0.486 (4)	0.1692 (8)	0.402 (2)	0.079*
O2	0.8321 (2)	0.16245 (4)	0.35918 (14)	0.0591 (4)
C14	0.8413 (2)	0.40231 (5)	0.24825 (13)	0.0279 (3)
H14	0.7919	0.4287	0.2851	0.034*
C15	1.1000 (2)	0.39814 (5)	0.29262 (14)	0.0287 (3)
H15A	1.1388	0.396	0.3794	0.034*
H15B	1.1528	0.3714	0.2607	0.034*
C16	1.2209 (3)	0.43702 (5)	0.25518 (15)	0.0344 (3)
H16A	1.1794	0.4634	0.2935	0.041*
H16B	1.3877	0.433	0.2813	0.041*
C17	1.1566 (3)	0.44292 (6)	0.12276 (15)	0.0396 (4)
H17A	1.2105	0.4177	0.0846	0.048*
H17B	1.2323	0.4691	0.1013	0.048*
C18	0.8999 (3)	0.44739 (6)	0.07856 (16)	0.0417 (4)
H18A	0.8617	0.4497	−0.0082	0.05*
H18B	0.8481	0.4742	0.1107	0.05*
C19	0.7764 (3)	0.40855 (6)	0.11536 (14)	0.0356 (4)
H19A	0.6098	0.413	0.0895	0.043*
H19B	0.8159	0.3822	0.0764	0.043*
C20	0.7233 (2)	0.36379 (5)	0.28708 (14)	0.0308 (3)
O3	0.7352 (3)	0.36357 (4)	0.40064 (11)	0.0509 (4)
H3	0.670 (4)	0.3407 (8)	0.422 (2)	0.076*
O4	0.6263 (2)	0.33594 (4)	0.22225 (11)	0.0529 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0324 (7)	0.0342 (8)	0.0228 (7)	−0.0031 (6)	0.0125 (6)	−0.0034 (6)
C2	0.0293 (7)	0.0386 (9)	0.0294 (8)	−0.0074 (6)	0.0055 (6)	−0.0089 (6)
C3	0.0344 (8)	0.0332 (8)	0.0321 (8)	0.0091 (6)	0.0029 (6)	0.0082 (6)
C4	0.0263 (7)	0.0364 (8)	0.0269 (7)	−0.0072 (6)	0.0033 (6)	−0.0009 (6)
C5	0.0364 (8)	0.0292 (8)	0.0408 (9)	0.0109 (6)	0.0082 (7)	0.0063 (7)
C6	0.0361 (8)	0.0447 (9)	0.0246 (7)	−0.0013 (7)	0.0139 (6)	−0.0036 (6)
N1	0.0316 (6)	0.0251 (6)	0.0264 (6)	0.0005 (5)	0.0093 (5)	−0.0032 (5)
N2	0.0338 (6)	0.0268 (6)	0.0270 (6)	−0.0038 (5)	0.0107 (5)	0.0003 (5)
N3	0.0306 (6)	0.0422 (8)	0.0198 (6)	−0.0001 (5)	0.0020 (5)	0.0003 (5)
N4	0.0227 (6)	0.0395 (7)	0.0323 (7)	0.0041 (5)	0.0085 (5)	0.0014 (5)
C7	0.0379 (8)	0.0244 (7)	0.0277 (7)	0.0014 (6)	0.0101 (6)	0.0006 (6)
C8	0.0314 (7)	0.0335 (8)	0.0342 (8)	−0.0019 (6)	0.0066 (6)	−0.0040 (6)
C9	0.0488 (10)	0.0430 (10)	0.0402 (9)	−0.0087 (8)	0.0122 (8)	−0.0146 (8)
C10	0.0587 (11)	0.0427 (10)	0.0502 (11)	−0.0010 (8)	0.0262 (9)	−0.0165 (8)
C11	0.0467 (10)	0.0370 (9)	0.0612 (12)	0.0143 (8)	0.0186 (9)	−0.0013 (8)
C12	0.0368 (9)	0.0422 (10)	0.0437 (10)	0.0099 (7)	0.0009 (7)	−0.0072 (8)
C13	0.0374 (8)	0.0271 (7)	0.0276 (7)	−0.0004 (6)	0.0073 (6)	−0.0009 (6)
O1	0.0505 (7)	0.0390 (7)	0.0771 (10)	−0.0104 (6)	0.0326 (7)	−0.0273 (7)
O2	0.0468 (7)	0.0409 (7)	0.0920 (11)	−0.0104 (6)	0.0209 (7)	−0.0218 (7)
C14	0.0265 (7)	0.0249 (7)	0.0334 (8)	−0.0015 (5)	0.0089 (6)	0.0010 (6)
C15	0.0280 (7)	0.0234 (7)	0.0335 (8)	−0.0005 (6)	0.0045 (6)	0.0015 (6)
C16	0.0287 (7)	0.0300 (8)	0.0442 (9)	−0.0059 (6)	0.0076 (7)	0.0022 (7)
C17	0.0371 (8)	0.0401 (9)	0.0442 (9)	−0.0088 (7)	0.0148 (7)	0.0069 (7)
C18	0.0417 (9)	0.0438 (10)	0.0386 (9)	−0.0015 (7)	0.0076 (7)	0.0139 (7)
C19	0.0274 (7)	0.0431 (9)	0.0350 (8)	−0.0038 (6)	0.0048 (6)	0.0073 (7)
C20	0.0288 (7)	0.0301 (8)	0.0352 (8)	−0.0036 (6)	0.0111 (6)	−0.0012 (6)
O3	0.0757 (9)	0.0449 (7)	0.0332 (6)	−0.0319 (7)	0.0148 (6)	−0.0005 (5)
O4	0.0721 (9)	0.0471 (8)	0.0427 (7)	−0.0303 (7)	0.0199 (7)	−0.0112 (6)

Geometric parameters (Å, º)

C1—N1	1.4718 (18)	C9—H9B	0.99
C1—N2	1.4756 (18)	C10—C11	1.513 (3)
C1—H1A	0.99	C10—H10A	0.99
C1—H1B	0.99	C10—H10B	0.99
C2—N3	1.456 (2)	C11—C12	1.525 (2)
C2—N2	1.4824 (19)	C11—H11A	0.99
C2—H2A	0.99	C11—H11B	0.99
C2—H2B	0.99	C12—H12A	0.99
C3—N3	1.459 (2)	C12—H12B	0.99
C3—N1	1.4780 (19)	C13—O2	1.2079 (19)
C3—H3A	0.99	C13—O1	1.3000 (19)
C3—H3B	0.99	O1—H1	0.97 (3)
C4—N4	1.458 (2)	C14—C20	1.510 (2)
C4—N1	1.4758 (18)	C14—C19	1.526 (2)
C4—H4A	0.99	C14—C15	1.5324 (19)
C4—H4B	0.99	C14—H14	1
C5—N4	1.456 (2)	C15—C16	1.522 (2)
C5—N2	1.4812 (19)	C15—H15A	0.99
C5—H5A	0.99	C15—H15B	0.99
C5—H5B	0.99	C16—C17	1.519 (2)
C6—N4	1.4670 (19)	C16—H16A	0.99
C6—N3	1.4713 (19)	C16—H16B	0.99
C6—H6A	0.99	C17—C18	1.521 (2)
C6—H6B	0.99	C17—H17A	0.99
C7—C13	1.512 (2)	C17—H17B	0.99
C7—C12	1.518 (2)	C18—C19	1.527 (2)
C7—C8	1.529 (2)	C18—H18A	0.99
C7—H7	1	C18—H18B	0.99
C8—C9	1.522 (2)	C19—H19A	0.99
C8—H8A	0.99	C19—H19B	0.99
C8—H8B	0.99	C20—O4	1.2057 (19)
C9—C10	1.519 (3)	C20—O3	1.3141 (19)
C9—H9A	0.99	O3—H3	0.87 (3)
N1—C1—N2	111.34 (11)	C8—C9—H9B	109.3
N1—C1—H1A	109.4	H9A—C9—H9B	107.9
N2—C1—H1A	109.4	C11—C10—C9	111.38 (15)
N1—C1—H1B	109.4	C11—C10—H10A	109.4
N2—C1—H1B	109.4	C9—C10—H10A	109.4
H1A—C1—H1B	108	C11—C10—H10B	109.4
N3—C2—N2	111.89 (11)	C9—C10—H10B	109.4
N3—C2—H2A	109.2	H10A—C10—H10B	108
N2—C2—H2A	109.2	C10—C11—C12	111.09 (15)
N3—C2—H2B	109.2	C10—C11—H11A	109.4
N2—C2—H2B	109.2	C12—C11—H11A	109.4
H2A—C2—H2B	107.9	C10—C11—H11B	109.4
N3—C3—N1	111.95 (12)	C12—C11—H11B	109.4
N3—C3—H3A	109.2	H11A—C11—H11B	108
N1—C3—H3A	109.2	C7—C12—C11	111.21 (14)
N3—C3—H3B	109.2	C7—C12—H12A	109.4
N1—C3—H3B	109.2	C11—C12—H12A	109.4
H3A—C3—H3B	107.9	C7—C12—H12B	109.4
N4—C4—N1	111.69 (11)	C11—C12—H12B	109.4
N4—C4—H4A	109.3	H12A—C12—H12B	108
N1—C4—H4A	109.3	O2—C13—O1	122.33 (15)
N4—C4—H4B	109.3	O2—C13—C7	123.72 (14)
N1—C4—H4B	109.3	O1—C13—C7	113.95 (13)
H4A—C4—H4B	107.9	C13—O1—H1	109.1 (15)
N4—C5—N2	112.12 (12)	C20—C14—C19	112.25 (12)
N4—C5—H5A	109.2	C20—C14—C15	110.26 (12)
N2—C5—H5A	109.2	C19—C14—C15	110.95 (12)
N4—C5—H5B	109.2	C20—C14—H14	107.7
N2—C5—H5B	109.2	C19—C14—H14	107.7
H5A—C5—H5B	107.9	C15—C14—H14	107.7
N4—C6—N3	112.23 (11)	C16—C15—C14	110.76 (12)
N4—C6—H6A	109.2	C16—C15—H15A	109.5
N3—C6—H6A	109.2	C14—C15—H15A	109.5
N4—C6—H6B	109.2	C16—C15—H15B	109.5
N3—C6—H6B	109.2	C14—C15—H15B	109.5
H6A—C6—H6B	107.9	H15A—C15—H15B	108.1
C1—N1—C4	108.76 (11)	C17—C16—C15	111.24 (13)
C1—N1—C3	107.97 (12)	C17—C16—H16A	109.4
C4—N1—C3	108.14 (11)	C15—C16—H16A	109.4
C1—N2—C5	107.78 (12)	C17—C16—H16B	109.4
C1—N2—C2	108.11 (12)	C15—C16—H16B	109.4
C5—N2—C2	108.14 (11)	H16A—C16—H16B	108
C2—N3—C3	108.53 (12)	C16—C17—C18	110.95 (13)
C2—N3—C6	108.22 (12)	C16—C17—H17A	109.5
C3—N3—C6	108.15 (12)	C18—C17—H17A	109.4
C5—N4—C4	108.49 (12)	C16—C17—H17B	109.4
C5—N4—C6	108.41 (12)	C18—C17—H17B	109.5
C4—N4—C6	108.25 (12)	H17A—C17—H17B	108
C13—C7—C12	110.92 (13)	C17—C18—C19	110.97 (14)
C13—C7—C8	110.46 (12)	C17—C18—H18A	109.4
C12—C7—C8	110.68 (13)	C19—C18—H18A	109.4
C13—C7—H7	108.2	C17—C18—H18B	109.4
C12—C7—H7	108.2	C19—C18—H18B	109.4
C8—C7—H7	108.2	H18A—C18—H18B	108
C9—C8—C7	111.43 (13)	C14—C19—C18	111.10 (13)
C9—C8—H8A	109.3	C14—C19—H19A	109.4
C7—C8—H8A	109.3	C18—C19—H19A	109.4
C9—C8—H8B	109.3	C14—C19—H19B	109.4
C7—C8—H8B	109.3	C18—C19—H19B	109.4
H8A—C8—H8B	108	H19A—C19—H19B	108
C10—C9—C8	111.82 (14)	O4—C20—O3	122.54 (14)
C10—C9—H9A	109.3	O4—C20—C14	124.57 (14)
C8—C9—H9A	109.3	O3—C20—C14	112.89 (13)
C10—C9—H9B	109.3	C20—O3—H3	111.9 (16)
N2—C1—N1—C4	58.29 (15)	C13—C7—C8—C9	178.13 (13)
N2—C1—N1—C3	−58.83 (15)	C12—C7—C8—C9	54.88 (18)
N4—C4—N1—C1	−58.43 (15)	C7—C8—C9—C10	−54.1 (2)
N4—C4—N1—C3	58.57 (15)	C8—C9—C10—C11	54.4 (2)
N3—C3—N1—C1	59.13 (15)	C9—C10—C11—C12	−55.4 (2)
N3—C3—N1—C4	−58.39 (16)	C13—C7—C12—C11	−179.17 (14)
N1—C1—N2—C5	−58.10 (15)	C8—C7—C12—C11	−56.18 (19)
N1—C1—N2—C2	58.57 (15)	C10—C11—C12—C7	56.7 (2)
N4—C5—N2—C1	58.98 (16)	C12—C7—C13—O2	13.2 (2)
N4—C5—N2—C2	−57.67 (16)	C8—C7—C13—O2	−109.90 (18)
N3—C2—N2—C1	−58.51 (15)	C12—C7—C13—O1	−166.83 (14)
N3—C2—N2—C5	57.93 (16)	C8—C7—C13—O1	70.06 (17)
N2—C2—N3—C3	58.66 (15)	C20—C14—C15—C16	−179.37 (12)
N2—C2—N3—C6	−58.49 (15)	C19—C14—C15—C16	55.64 (17)
N1—C3—N3—C2	−59.06 (16)	C14—C15—C16—C17	−56.27 (17)
N1—C3—N3—C6	58.13 (16)	C15—C16—C17—C18	56.71 (18)
N4—C6—N3—C2	58.92 (16)	C16—C17—C18—C19	−56.29 (19)
N4—C6—N3—C3	−58.47 (17)	C20—C14—C19—C18	−179.42 (13)
N2—C5—N4—C4	−59.31 (16)	C15—C14—C19—C18	−55.56 (17)
N2—C5—N4—C6	58.02 (16)	C17—C18—C19—C14	55.91 (19)
N1—C4—N4—C5	58.65 (15)	C19—C14—C20—O4	14.2 (2)
N1—C4—N4—C6	−58.79 (15)	C15—C14—C20—O4	−110.04 (18)
N3—C6—N4—C5	−58.64 (17)	C19—C14—C20—O3	−165.45 (14)
N3—C6—N4—C4	58.85 (16)	C15—C14—C20—O3	70.30 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.97 (3)	1.70 (3)	2.6684 (17)	177 (2)
O3—H3···N2	0.87 (3)	1.81 (3)	2.6771 (17)	174 (2)
C2—H2A···N4^i	0.99	2.63	3.5737 (19)	161
C3—H3B···O4^ii	0.99	2.68	3.5007 (19)	140
C4—H4A···N3^iii	0.99	2.67	3.5913 (19)	154
C6—H6A···O4^iv	0.99	2.5	3.442 (2)	160
C6—H6B···O2^iv	0.99	2.4	3.361 (2)	163

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, −y+1/2, z+1/2.

(2) bis(para-flourobenzoic acid).(hexamethylenetetramine)

Crystal data

C6H12N4·2(C7H5FO2)	F(000) = 880
Mr = 420.42	Dx = 1.443 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6303 reflections
a = 6.1529 (1) Å	θ = 2.9–28.2°
b = 26.9424 (6) Å	µ = 0.12 mm^−1
c = 11.8758 (3) Å	T = 173 K
β = 100.553 (1)°	Block, colourless
V = 1935.40 (7) Å^3	0.5 × 0.5 × 0.24 mm
Z = 4

Data collection

Bruker APEX II CCD area detector diffractometer	4058 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 28°, θmin = 1.5°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −8→8
Tmin = 0.95, Tmax = 0.97	k = −35→35
30806 measured reflections	l = −15→15
4670 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 0.6252P] where P = (Fo^2 + 2Fc^2)/3
4670 reflections	(Δ/σ)max < 0.001
277 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.54745 (18)	0.25571 (4)	0.51686 (9)	0.0255 (2)
H1A	0.4704	0.2617	0.4373	0.031*
H1B	0.7036	0.2476	0.5147	0.031*
C2	0.65179 (19)	0.29109 (5)	0.70436 (10)	0.0303 (2)
H2A	0.8093	0.2835	0.7047	0.036*
H2B	0.6453	0.3212	0.7515	0.036*
C3	0.5617 (2)	0.20546 (4)	0.68432 (10)	0.0286 (2)
H3A	0.4947	0.177	0.7182	0.034*
H3B	0.7183	0.1973	0.6837	0.034*
C4	0.21040 (18)	0.22647 (5)	0.56750 (10)	0.0294 (2)
H4A	0.1305	0.2321	0.4883	0.035*
H4B	0.1382	0.1985	0.6002	0.035*
C5	0.3029 (2)	0.31203 (4)	0.58638 (11)	0.0302 (2)
H5A	0.2925	0.3426	0.6315	0.036*
H5B	0.2246	0.3181	0.5071	0.036*
C6	0.3170 (2)	0.26175 (5)	0.75236 (10)	0.0327 (3)
H6A	0.2459	0.2339	0.7862	0.039*
H6B	0.3078	0.2915	0.8	0.039*
N1	0.44373 (15)	0.21332 (3)	0.56502 (8)	0.02355 (19)
N2	0.53854 (16)	0.30112 (4)	0.58518 (8)	0.0257 (2)
N3	0.55096 (17)	0.24960 (4)	0.75496 (8)	0.0294 (2)
N4	0.19563 (16)	0.27115 (4)	0.63584 (9)	0.0300 (2)
C7	0.70650 (18)	0.09617 (4)	0.32665 (9)	0.0236 (2)
C8	0.53199 (18)	0.08334 (4)	0.23956 (10)	0.0259 (2)
H8	0.3879	0.0956	0.2412	0.031*
C9	0.5659 (2)	0.05288 (4)	0.15041 (10)	0.0293 (2)
H9	0.4472	0.044	0.0908	0.035*
C10	0.7764 (2)	0.03599 (4)	0.15103 (11)	0.0311 (3)
C11	0.9536 (2)	0.04833 (5)	0.23458 (12)	0.0358 (3)
H11	1.0975	0.0362	0.2316	0.043*
C12	0.91777 (19)	0.07882 (4)	0.32310 (11)	0.0318 (3)
H12	1.038	0.0879	0.3817	0.038*
C13	0.67277 (19)	0.12973 (4)	0.42198 (9)	0.0260 (2)
O1	0.46490 (14)	0.14116 (3)	0.42147 (7)	0.0322 (2)
H1	0.462 (3)	0.1666 (8)	0.4838 (18)	0.07*
O2	0.82604 (15)	0.14564 (4)	0.49163 (8)	0.0413 (2)
F1	0.81283 (14)	0.00618 (3)	0.06427 (7)	0.0465 (2)
C14	0.80223 (19)	0.39997 (4)	0.30471 (10)	0.0266 (2)
C15	1.0190 (2)	0.41335 (4)	0.34873 (10)	0.0283 (2)
H15	1.0822	0.4049	0.4254	0.034*
C16	1.1439 (2)	0.43886 (5)	0.28192 (11)	0.0337 (3)
H16	1.2931	0.4476	0.311	0.04*
C17	1.0450 (2)	0.45107 (5)	0.17208 (11)	0.0377 (3)
C18	0.8302 (2)	0.43930 (5)	0.12611 (11)	0.0401 (3)
H18	0.7668	0.449	0.0503	0.048*
C19	0.7081 (2)	0.41293 (5)	0.19266 (11)	0.0340 (3)
H19	0.5602	0.4036	0.1621	0.041*
C20	0.67173 (19)	0.36921 (4)	0.37260 (11)	0.0294 (2)
O3	0.75605 (18)	0.36740 (4)	0.48286 (8)	0.0443 (3)
H3	0.674 (4)	0.3467 (9)	0.519 (2)	0.088*
O4	0.50658 (16)	0.34704 (4)	0.32976 (9)	0.0473 (3)
F2	1.16690 (17)	0.47596 (4)	0.10609 (8)	0.0590 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0286 (5)	0.0288 (5)	0.0211 (5)	−0.0013 (4)	0.0099 (4)	−0.0010 (4)
C2	0.0271 (5)	0.0359 (6)	0.0265 (6)	−0.0056 (5)	0.0014 (4)	−0.0063 (5)
C3	0.0332 (6)	0.0286 (6)	0.0232 (5)	0.0043 (4)	0.0026 (4)	0.0029 (4)
C4	0.0223 (5)	0.0342 (6)	0.0311 (6)	−0.0050 (4)	0.0036 (4)	−0.0031 (5)
C5	0.0310 (6)	0.0271 (6)	0.0331 (6)	0.0057 (4)	0.0071 (5)	0.0017 (4)
C6	0.0383 (6)	0.0372 (6)	0.0265 (6)	−0.0008 (5)	0.0167 (5)	−0.0021 (5)
N1	0.0256 (4)	0.0246 (4)	0.0206 (4)	−0.0010 (3)	0.0045 (3)	−0.0018 (3)
N2	0.0277 (5)	0.0259 (5)	0.0247 (5)	−0.0036 (4)	0.0079 (4)	−0.0012 (4)
N3	0.0342 (5)	0.0340 (5)	0.0194 (5)	0.0001 (4)	0.0032 (4)	−0.0007 (4)
N4	0.0233 (4)	0.0347 (5)	0.0338 (5)	0.0011 (4)	0.0098 (4)	−0.0016 (4)
C7	0.0264 (5)	0.0215 (5)	0.0224 (5)	−0.0023 (4)	0.0037 (4)	0.0010 (4)
C8	0.0236 (5)	0.0276 (5)	0.0263 (5)	−0.0011 (4)	0.0039 (4)	−0.0019 (4)
C9	0.0313 (6)	0.0307 (6)	0.0251 (6)	−0.0037 (4)	0.0029 (4)	−0.0044 (4)
C10	0.0386 (6)	0.0258 (5)	0.0316 (6)	−0.0016 (5)	0.0134 (5)	−0.0052 (4)
C11	0.0277 (6)	0.0329 (6)	0.0474 (8)	0.0036 (5)	0.0086 (5)	−0.0043 (5)
C12	0.0264 (5)	0.0306 (6)	0.0357 (6)	0.0008 (4)	−0.0014 (5)	−0.0023 (5)
C13	0.0303 (5)	0.0241 (5)	0.0224 (5)	−0.0026 (4)	0.0019 (4)	0.0005 (4)
O1	0.0309 (4)	0.0358 (5)	0.0295 (4)	0.0000 (3)	0.0042 (3)	−0.0115 (3)
O2	0.0354 (5)	0.0477 (6)	0.0366 (5)	−0.0029 (4)	−0.0043 (4)	−0.0162 (4)
F1	0.0522 (5)	0.0457 (5)	0.0457 (5)	0.0005 (4)	0.0201 (4)	−0.0190 (4)
C14	0.0316 (6)	0.0207 (5)	0.0281 (6)	0.0004 (4)	0.0069 (4)	−0.0021 (4)
C15	0.0327 (6)	0.0233 (5)	0.0284 (6)	0.0004 (4)	0.0043 (4)	0.0017 (4)
C16	0.0326 (6)	0.0306 (6)	0.0384 (7)	−0.0032 (5)	0.0076 (5)	0.0016 (5)
C17	0.0487 (7)	0.0343 (6)	0.0336 (7)	−0.0058 (5)	0.0167 (6)	0.0027 (5)
C18	0.0526 (8)	0.0415 (7)	0.0249 (6)	−0.0042 (6)	0.0038 (5)	0.0021 (5)
C19	0.0356 (6)	0.0335 (6)	0.0307 (6)	−0.0023 (5)	0.0006 (5)	−0.0018 (5)
C20	0.0293 (6)	0.0252 (5)	0.0334 (6)	−0.0009 (4)	0.0049 (5)	0.0003 (4)
O3	0.0547 (6)	0.0477 (6)	0.0301 (5)	−0.0260 (5)	0.0066 (4)	0.0032 (4)
O4	0.0370 (5)	0.0539 (6)	0.0463 (6)	−0.0170 (4)	−0.0050 (4)	0.0124 (5)
F2	0.0657 (6)	0.0707 (6)	0.0448 (5)	−0.0191 (5)	0.0215 (4)	0.0149 (4)

Geometric parameters (Å, º)

C1—N1	1.4739 (14)	C8—C9	1.3853 (16)
C1—N2	1.4746 (14)	C8—H8	0.95
C1—H1A	0.99	C9—C10	1.3714 (17)
C1—H1B	0.99	C9—H9	0.95
C2—N3	1.4602 (15)	C10—F1	1.3571 (14)
C2—N2	1.4834 (15)	C10—C11	1.3740 (18)
C2—H2A	0.99	C11—C12	1.3832 (18)
C2—H2B	0.99	C11—H11	0.95
C3—N3	1.4639 (15)	C12—H12	0.95
C3—N1	1.4840 (14)	C13—O2	1.2130 (14)
C3—H3A	0.99	C13—O1	1.3145 (14)
C3—H3B	0.99	O1—H1	1.01 (2)
C4—N4	1.4639 (16)	C14—C15	1.3880 (16)
C4—N1	1.4842 (14)	C14—C19	1.3948 (17)
C4—H4A	0.99	C14—C20	1.4895 (16)
C4—H4B	0.99	C15—C16	1.3840 (17)
C5—N4	1.4616 (15)	C15—H15	0.95
C5—N2	1.4819 (15)	C16—C17	1.3745 (19)
C5—H5A	0.99	C16—H16	0.95
C5—H5B	0.99	C17—F2	1.3571 (15)
C6—N4	1.4691 (16)	C17—C18	1.371 (2)
C6—N3	1.4709 (16)	C18—C19	1.3824 (19)
C6—H6A	0.99	C18—H18	0.95
C6—H6B	0.99	C19—H19	0.95
C7—C12	1.3893 (16)	C20—O4	1.2079 (15)
C7—C8	1.3912 (15)	C20—O3	1.3181 (15)
C7—C13	1.4928 (15)	O3—H3	0.91 (2)
N1—C1—N2	111.53 (8)	C5—N4—C6	108.62 (9)
N1—C1—H1A	109.3	C4—N4—C6	107.94 (10)
N2—C1—H1A	109.3	C12—C7—C8	119.53 (10)
N1—C1—H1B	109.3	C12—C7—C13	119.19 (10)
N2—C1—H1B	109.3	C8—C7—C13	121.25 (10)
H1A—C1—H1B	108	C9—C8—C7	120.77 (10)
N3—C2—N2	111.80 (9)	C9—C8—H8	119.6
N3—C2—H2A	109.3	C7—C8—H8	119.6
N2—C2—H2A	109.3	C10—C9—C8	117.82 (11)
N3—C2—H2B	109.3	C10—C9—H9	121.1
N2—C2—H2B	109.3	C8—C9—H9	121.1
H2A—C2—H2B	107.9	F1—C10—C9	118.64 (11)
N3—C3—N1	111.45 (9)	F1—C10—C11	118.15 (11)
N3—C3—H3A	109.3	C9—C10—C11	123.20 (11)
N1—C3—H3A	109.3	C10—C11—C12	118.45 (11)
N3—C3—H3B	109.3	C10—C11—H11	120.8
N1—C3—H3B	109.3	C12—C11—H11	120.8
H3A—C3—H3B	108	C11—C12—C7	120.22 (11)
N4—C4—N1	111.45 (9)	C11—C12—H12	119.9
N4—C4—H4A	109.3	C7—C12—H12	119.9
N1—C4—H4A	109.3	O2—C13—O1	123.68 (11)
N4—C4—H4B	109.3	O2—C13—C7	122.17 (11)
N1—C4—H4B	109.3	O1—C13—C7	114.13 (9)
H4A—C4—H4B	108	C13—O1—H1	107.8 (11)
N4—C5—N2	111.66 (9)	C15—C14—C19	119.77 (11)
N4—C5—H5A	109.3	C15—C14—C20	121.11 (10)
N2—C5—H5A	109.3	C19—C14—C20	119.01 (11)
N4—C5—H5B	109.3	C16—C15—C14	120.61 (11)
N2—C5—H5B	109.3	C16—C15—H15	119.7
H5A—C5—H5B	108	C14—C15—H15	119.7
N4—C6—N3	112.64 (9)	C17—C16—C15	117.84 (12)
N4—C6—H6A	109.1	C17—C16—H16	121.1
N3—C6—H6A	109.1	C15—C16—H16	121.1
N4—C6—H6B	109.1	F2—C17—C18	118.59 (12)
N3—C6—H6B	109.1	F2—C17—C16	118.09 (12)
H6A—C6—H6B	107.8	C18—C17—C16	123.32 (12)
C1—N1—C3	108.08 (9)	C17—C18—C19	118.43 (12)
C1—N1—C4	108.18 (9)	C17—C18—H18	120.8
C3—N1—C4	108.71 (9)	C19—C18—H18	120.8
C1—N2—C5	107.76 (9)	C18—C19—C14	120.00 (12)
C1—N2—C2	108.40 (9)	C18—C19—H19	120
C5—N2—C2	108.44 (9)	C14—C19—H19	120
C2—N3—C3	108.60 (9)	O4—C20—O3	123.22 (12)
C2—N3—C6	107.99 (9)	O4—C20—C14	122.85 (11)
C3—N3—C6	108.38 (9)	O3—C20—C14	113.90 (10)
C5—N4—C4	108.57 (9)	C20—O3—H3	109.9 (15)
N2—C1—N1—C3	−58.67 (11)	C7—C8—C9—C10	−0.08 (17)
N2—C1—N1—C4	58.87 (11)	C8—C9—C10—F1	−179.88 (11)
N3—C3—N1—C1	59.24 (12)	C8—C9—C10—C11	−0.80 (19)
N3—C3—N1—C4	−57.95 (12)	F1—C10—C11—C12	179.82 (11)
N4—C4—N1—C1	−58.59 (12)	C9—C10—C11—C12	0.7 (2)
N4—C4—N1—C3	58.54 (12)	C10—C11—C12—C7	0.21 (19)
N1—C1—N2—C5	−59.03 (11)	C8—C7—C12—C11	−1.06 (18)
N1—C1—N2—C2	58.13 (11)	C13—C7—C12—C11	−178.95 (11)
N4—C5—N2—C1	59.32 (12)	C12—C7—C13—O2	6.02 (17)
N4—C5—N2—C2	−57.82 (12)	C8—C7—C13—O2	−171.84 (11)
N3—C2—N2—C1	−58.18 (12)	C12—C7—C13—O1	−175.55 (10)
N3—C2—N2—C5	58.54 (12)	C8—C7—C13—O1	6.59 (15)
N2—C2—N3—C3	58.88 (12)	C19—C14—C15—C16	−0.92 (17)
N2—C2—N3—C6	−58.45 (12)	C20—C14—C15—C16	175.28 (11)
N1—C3—N3—C2	−59.43 (12)	C14—C15—C16—C17	1.11 (18)
N1—C3—N3—C6	57.65 (12)	C15—C16—C17—F2	−179.83 (12)
N4—C6—N3—C2	58.60 (12)	C15—C16—C17—C18	0.1 (2)
N4—C6—N3—C3	−58.88 (13)	F2—C17—C18—C19	178.50 (12)
N2—C5—N4—C4	−59.57 (12)	C16—C17—C18—C19	−1.4 (2)
N2—C5—N4—C6	57.56 (12)	C17—C18—C19—C14	1.6 (2)
N1—C4—N4—C5	59.01 (12)	C15—C14—C19—C18	−0.45 (18)
N1—C4—N4—C6	−58.56 (12)	C20—C14—C19—C18	−176.72 (12)
N3—C6—N4—C5	−58.35 (13)	C15—C14—C20—O4	−161.74 (12)
N3—C6—N4—C4	59.19 (12)	C19—C14—C20—O4	14.49 (18)
C12—C7—C8—C9	1.00 (17)	C15—C14—C20—O3	16.59 (16)
C13—C7—C8—C9	178.85 (10)	C19—C14—C20—O3	−167.18 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	1.01 (2)	1.60 (2)	2.6046 (12)	170 (2)
O3—H3···N2	0.91 (2)	1.75 (2)	2.6556 (13)	173 (2)
C2—H2A···N4^i	0.99	2.67	3.6257 (15)	162
C3—H3B···O4^ii	0.99	2.54	3.2781 (15)	131
C9—H9···F1^iii	0.95	2.59	3.5051 (14)	162
C19—H19···O2^iv	0.95	2.62	3.4148 (16)	141
C2—H2A···N4^i	0.99	2.67	3.6257 (15)	162
C4—H4A···N3^iv	0.99	2.77	3.7176 (15)	161

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+1, −y, −z; (iv) x−1/2, −y+1/2, z−1/2.

(3) bis(toluidine carboxylic acid).(hexamethylenetetramine)

Crystal data

C6H12N4·2(C8H8O2)	F(000) = 880
Mr = 412.48	Dx = 1.312 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1336 reflections
a = 6.1754 (18) Å	θ = 2.9–28.4°
b = 28.234 (7) Å	µ = 0.09 mm^−1
c = 12.154 (3) Å	T = 173 K
β = 99.869 (15)°	Plate, colourless
V = 2087.8 (9) Å^3	0.3 × 0.24 × 0.05 mm
Z = 4

Data collection

Bruker APEX II CCD area detector diffractometer	1948 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.094
ω scans	θmax = 25.5°, θmin = 1.4°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −7→5
Tmin = 0.97, Tmax = 0.99	k = −29→34
10621 measured reflections	l = −14→14
3866 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.121	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.366	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
3866 reflections	(Δ/σ)max < 0.001
273 parameters	Δρmax = 0.87 e Å^−3
0 restraints	Δρmin = −0.55 e Å^−3

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2161 (10)	0.24714 (18)	0.3143 (5)	0.0270 (14)
H1A	0.1433	0.2406	0.2367	0.032*
H1B	0.3727	0.2542	0.3132	0.032*
C2	0.2197 (11)	0.2974 (2)	0.4740 (5)	0.0368 (16)
H2A	0.3763	0.3054	0.4754	0.044*
H2B	0.1489	0.3249	0.5042	0.044*
C3	0.3083 (10)	0.2154 (2)	0.5004 (5)	0.0354 (16)
H3A	0.2976	0.1873	0.548	0.043*
H3B	0.466	0.2222	0.5017	0.043*
C4	−0.0332 (10)	0.1951 (2)	0.3839 (6)	0.0385 (17)
H4A	−0.0464	0.1668	0.4303	0.046*
H4B	−0.1067	0.1881	0.3067	0.046*
C5	−0.1218 (10)	0.2767 (2)	0.3581 (6)	0.0382 (16)
H5A	−0.1954	0.3041	0.3866	0.046*
H5B	−0.1962	0.2704	0.2806	0.046*
C6	−0.0306 (11)	0.2459 (2)	0.5401 (5)	0.0385 (17)
H6A	−0.0465	0.2186	0.5893	0.046*
H6B	−0.1012	0.2736	0.5692	0.046*
N1	0.1998 (8)	0.20508 (17)	0.3841 (4)	0.0300 (13)
N2	0.1119 (8)	0.28861 (16)	0.3574 (4)	0.0274 (12)
N3	0.2045 (9)	0.25591 (18)	0.5448 (4)	0.0381 (14)
N4	−0.1441 (8)	0.2353 (2)	0.4273 (5)	0.0386 (14)
C7	0.3988 (10)	0.1078 (2)	0.1016 (5)	0.0292 (14)
C8	0.6121 (10)	0.0933 (2)	0.1299 (5)	0.0367 (16)
H8	0.6937	0.1007	0.2014	0.044*
C9	0.7099 (11)	0.0674 (2)	0.0535 (6)	0.0417 (18)
H9	0.858	0.0571	0.0731	0.05*
C10	0.5912 (12)	0.0568 (2)	−0.0506 (5)	0.0394 (17)
C11	0.3783 (13)	0.0722 (2)	−0.0789 (5)	0.0424 (18)
H11	0.2979	0.0652	−0.151	0.051*
C12	0.2792 (12)	0.0976 (2)	−0.0040 (5)	0.0379 (16)
H12	0.1314	0.1081	−0.0241	0.046*
C13	0.2881 (10)	0.1372 (2)	0.1787 (5)	0.0299 (14)
C14	0.6969 (13)	0.0287 (3)	−0.1324 (6)	0.056 (2)
H14A	0.6828	−0.0052	−0.1178	0.084*
H14B	0.8528	0.0371	−0.124	0.084*
H14C	0.6237	0.036	−0.2086	0.084*
O1	0.4019 (8)	0.14065 (16)	0.2790 (4)	0.0491 (14)
H1	0.3327	0.1573	0.3186	0.074*
O2	0.1130 (8)	0.15501 (19)	0.1498 (4)	0.0580 (16)
C15	0.3948 (10)	0.39169 (19)	0.1124 (5)	0.0254 (13)
C16	0.2243 (10)	0.4037 (2)	0.0250 (5)	0.0342 (15)
H16	0.0783	0.3937	0.0273	0.041*
C17	0.2680 (11)	0.4301 (2)	−0.0641 (5)	0.0383 (16)
H17	0.1517	0.4385	−0.1226	0.046*
C18	0.4779 (11)	0.4441 (2)	−0.0685 (5)	0.0333 (15)
C19	0.6460 (11)	0.4325 (2)	0.0167 (6)	0.0410 (18)
H19	0.7917	0.4426	0.0136	0.049*
C20	0.6034 (10)	0.4055 (2)	0.1092 (6)	0.0364 (16)
H20	0.7195	0.3972	0.1679	0.044*
C21	0.3455 (10)	0.3621 (2)	0.2084 (5)	0.0299 (14)
C22	0.5325 (13)	0.4718 (2)	−0.1665 (6)	0.051 (2)
H22A	0.6338	0.4976	−0.1391	0.076*
H22B	0.3974	0.485	−0.2095	0.076*
H22C	0.6019	0.4507	−0.2143	0.076*
O3	0.1429 (7)	0.35404 (15)	0.2081 (4)	0.0418 (12)
H3	0.1291	0.3375	0.2639	0.063*
O4	0.4955 (8)	0.34793 (17)	0.2798 (4)	0.0521 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.039 (4)	0.023 (3)	0.022 (3)	0.001 (3)	0.015 (3)	0.003 (2)
C2	0.051 (4)	0.033 (4)	0.029 (4)	−0.009 (3)	0.014 (3)	−0.004 (3)
C3	0.033 (3)	0.043 (4)	0.030 (4)	0.010 (3)	0.005 (3)	0.003 (3)
C4	0.038 (4)	0.036 (4)	0.044 (4)	−0.007 (3)	0.015 (3)	−0.009 (3)
C5	0.039 (4)	0.035 (4)	0.043 (4)	0.009 (3)	0.013 (3)	0.004 (3)
C6	0.061 (5)	0.032 (4)	0.031 (4)	−0.001 (3)	0.031 (4)	0.000 (3)
N1	0.038 (3)	0.027 (3)	0.028 (3)	0.000 (2)	0.013 (2)	0.002 (2)
N2	0.038 (3)	0.022 (3)	0.024 (3)	0.003 (2)	0.013 (2)	−0.002 (2)
N3	0.049 (3)	0.041 (3)	0.026 (3)	0.000 (3)	0.010 (3)	0.000 (2)
N4	0.036 (3)	0.040 (3)	0.043 (3)	0.002 (2)	0.016 (3)	0.002 (3)
C7	0.045 (4)	0.019 (3)	0.028 (3)	−0.001 (3)	0.018 (3)	0.003 (2)
C8	0.041 (4)	0.034 (4)	0.036 (4)	0.005 (3)	0.009 (3)	−0.001 (3)
C9	0.040 (4)	0.031 (4)	0.059 (5)	0.010 (3)	0.023 (4)	0.003 (3)
C10	0.066 (5)	0.025 (3)	0.034 (4)	0.002 (3)	0.028 (4)	0.007 (3)
C11	0.068 (5)	0.033 (4)	0.029 (4)	−0.002 (3)	0.016 (4)	−0.001 (3)
C12	0.053 (4)	0.027 (3)	0.037 (4)	0.004 (3)	0.017 (3)	0.002 (3)
C13	0.034 (4)	0.018 (3)	0.037 (4)	0.001 (3)	0.006 (3)	0.000 (3)
C14	0.091 (6)	0.040 (4)	0.049 (5)	0.006 (4)	0.042 (5)	−0.004 (3)
O1	0.062 (3)	0.046 (3)	0.038 (3)	0.025 (2)	0.004 (3)	−0.011 (2)
O2	0.041 (3)	0.075 (4)	0.054 (3)	0.023 (3)	−0.003 (3)	−0.028 (3)
C15	0.035 (3)	0.018 (3)	0.025 (3)	0.005 (2)	0.011 (3)	0.000 (2)
C16	0.035 (4)	0.021 (3)	0.047 (4)	−0.001 (3)	0.007 (3)	−0.001 (3)
C17	0.046 (4)	0.032 (4)	0.033 (4)	0.005 (3)	−0.005 (3)	0.000 (3)
C18	0.042 (4)	0.029 (3)	0.032 (4)	0.007 (3)	0.016 (3)	−0.005 (3)
C19	0.031 (4)	0.025 (4)	0.073 (5)	−0.003 (3)	0.024 (4)	−0.009 (3)
C20	0.029 (3)	0.033 (4)	0.044 (4)	0.002 (3)	−0.002 (3)	−0.002 (3)
C21	0.033 (3)	0.016 (3)	0.039 (4)	0.004 (3)	0.000 (3)	−0.002 (3)
C22	0.084 (6)	0.032 (4)	0.044 (4)	−0.006 (4)	0.034 (4)	0.001 (3)
O3	0.035 (3)	0.040 (3)	0.051 (3)	0.000 (2)	0.009 (2)	0.012 (2)
O4	0.051 (3)	0.053 (3)	0.048 (3)	−0.006 (2)	−0.002 (3)	0.021 (2)

Geometric parameters (Å, º)

C1—N1	1.473 (7)	C9—H9	0.95
C1—N2	1.475 (7)	C10—C11	1.371 (10)
C1—H1A	0.99	C10—C14	1.505 (8)
C1—H1B	0.99	C11—C12	1.383 (8)
C2—N3	1.467 (8)	C11—H11	0.95
C2—N2	1.480 (8)	C12—H12	0.95
C2—H2A	0.99	C13—O2	1.190 (7)
C2—H2B	0.99	C13—O1	1.302 (7)
C3—N3	1.460 (8)	C14—H14A	0.98
C3—N1	1.486 (8)	C14—H14B	0.98
C3—H3A	0.99	C14—H14C	0.98
C3—H3B	0.99	O1—H1	0.84
C4—N1	1.466 (7)	C15—C20	1.352 (8)
C4—N4	1.469 (8)	C15—C16	1.403 (8)
C4—H4A	0.99	C15—C21	1.508 (8)
C4—H4B	0.99	C16—C17	1.378 (9)
C5—N4	1.460 (8)	C16—H16	0.95
C5—N2	1.483 (8)	C17—C18	1.365 (9)
C5—H5A	0.99	C17—H17	0.95
C5—H5B	0.99	C18—C19	1.374 (9)
C6—N4	1.460 (8)	C18—C22	1.510 (8)
C6—N3	1.471 (8)	C19—C20	1.420 (9)
C6—H6A	0.99	C19—H19	0.95
C6—H6B	0.99	C20—H20	0.95
C7—C8	1.367 (9)	C21—O4	1.223 (7)
C7—C12	1.396 (9)	C21—O3	1.271 (7)
C7—C13	1.500 (8)	C22—H22A	0.98
C8—C9	1.397 (8)	C22—H22B	0.98
C8—H8	0.95	C22—H22C	0.98
C9—C10	1.383 (10)	O3—H3	0.84
N1—C1—N2	111.0 (4)	C7—C8—H8	120.1
N1—C1—H1A	109.4	C9—C8—H8	120.1
N2—C1—H1A	109.4	C10—C9—C8	120.0 (6)
N1—C1—H1B	109.4	C10—C9—H9	120
N2—C1—H1B	109.4	C8—C9—H9	120
H1A—C1—H1B	108	C11—C10—C9	119.8 (6)
N3—C2—N2	111.3 (5)	C11—C10—C14	120.4 (7)
N3—C2—H2A	109.4	C9—C10—C14	119.8 (7)
N2—C2—H2A	109.4	C10—C11—C12	120.8 (7)
N3—C2—H2B	109.4	C10—C11—H11	119.6
N2—C2—H2B	109.4	C12—C11—H11	119.6
H2A—C2—H2B	108	C11—C12—C7	119.2 (6)
N3—C3—N1	110.5 (5)	C11—C12—H12	120.4
N3—C3—H3A	109.6	C7—C12—H12	120.4
N1—C3—H3A	109.6	O2—C13—O1	124.1 (6)
N3—C3—H3B	109.6	O2—C13—C7	122.6 (6)
N1—C3—H3B	109.6	O1—C13—C7	113.3 (5)
H3A—C3—H3B	108.1	C10—C14—H14A	109.5
N1—C4—N4	111.7 (5)	C10—C14—H14B	109.5
N1—C4—H4A	109.3	H14A—C14—H14B	109.5
N4—C4—H4A	109.3	C10—C14—H14C	109.5
N1—C4—H4B	109.3	H14A—C14—H14C	109.5
N4—C4—H4B	109.3	H14B—C14—H14C	109.5
H4A—C4—H4B	107.9	C13—O1—H1	109.5
N4—C5—N2	111.9 (5)	C20—C15—C16	120.2 (5)
N4—C5—H5A	109.2	C20—C15—C21	120.1 (6)
N2—C5—H5A	109.2	C16—C15—C21	119.7 (5)
N4—C5—H5B	109.2	C17—C16—C15	120.2 (6)
N2—C5—H5B	109.2	C17—C16—H16	119.9
H5A—C5—H5B	107.9	C15—C16—H16	119.9
N4—C6—N3	112.8 (4)	C18—C17—C16	120.2 (6)
N4—C6—H6A	109	C18—C17—H17	119.9
N3—C6—H6A	109	C16—C17—H17	119.9
N4—C6—H6B	109	C17—C18—C19	120.1 (6)
N3—C6—H6B	109	C17—C18—C22	121.5 (6)
H6A—C6—H6B	107.8	C19—C18—C22	118.4 (6)
C4—N1—C1	108.5 (5)	C18—C19—C20	120.4 (6)
C4—N1—C3	108.8 (4)	C18—C19—H19	119.8
C1—N1—C3	109.0 (5)	C20—C19—H19	119.8
C1—N2—C2	108.8 (5)	C15—C20—C19	118.9 (6)
C1—N2—C5	107.8 (4)	C15—C20—H20	120.5
C2—N2—C5	108.2 (4)	C19—C20—H20	120.5
C3—N3—C2	109.5 (5)	O4—C21—O3	124.7 (6)
C3—N3—C6	109.2 (5)	O4—C21—C15	120.1 (6)
C2—N3—C6	107.1 (5)	O3—C21—C15	115.2 (5)
C6—N4—C5	107.5 (5)	C18—C22—H22A	109.5
C6—N4—C4	108.5 (5)	C18—C22—H22B	109.5
C5—N4—C4	108.3 (5)	H22A—C22—H22B	109.5
C8—C7—C12	120.3 (6)	C18—C22—H22C	109.5
C8—C7—C13	122.1 (6)	H22A—C22—H22C	109.5
C12—C7—C13	117.5 (6)	H22B—C22—H22C	109.5
C7—C8—C9	119.8 (7)	C21—O3—H3	109.5
N4—C4—N1—C1	−59.2 (6)	C7—C8—C9—C10	0.3 (9)
N4—C4—N1—C3	59.3 (7)	C8—C9—C10—C11	0.7 (9)
N2—C1—N1—C4	59.5 (6)	C8—C9—C10—C14	−179.7 (6)
N2—C1—N1—C3	−58.8 (6)	C9—C10—C11—C12	−0.9 (9)
N3—C3—N1—C4	−59.2 (6)	C14—C10—C11—C12	179.4 (6)
N3—C3—N1—C1	59.0 (6)	C10—C11—C12—C7	0.2 (9)
N1—C1—N2—C2	58.1 (6)	C8—C7—C12—C11	0.8 (9)
N1—C1—N2—C5	−59.0 (6)	C13—C7—C12—C11	177.6 (5)
N3—C2—N2—C1	−58.0 (6)	C8—C7—C13—O2	170.2 (6)
N3—C2—N2—C5	58.9 (6)	C12—C7—C13—O2	−6.5 (9)
N4—C5—N2—C1	59.1 (6)	C8—C7—C13—O1	−10.2 (8)
N4—C5—N2—C2	−58.4 (6)	C12—C7—C13—O1	173.0 (5)
N1—C3—N3—C2	−59.0 (6)	C20—C15—C16—C17	−0.6 (9)
N1—C3—N3—C6	57.9 (6)	C21—C15—C16—C17	−178.9 (5)
N2—C2—N3—C3	58.9 (7)	C15—C16—C17—C18	0.8 (9)
N2—C2—N3—C6	−59.3 (6)	C16—C17—C18—C19	−0.8 (9)
N4—C6—N3—C3	−57.9 (6)	C16—C17—C18—C22	178.2 (5)
N4—C6—N3—C2	60.6 (6)	C17—C18—C19—C20	0.6 (9)
N3—C6—N4—C5	−60.1 (6)	C22—C18—C19—C20	−178.5 (5)
N3—C6—N4—C4	56.9 (6)	C16—C15—C20—C19	0.4 (9)
N2—C5—N4—C6	58.3 (6)	C21—C15—C20—C19	178.7 (5)
N2—C5—N4—C4	−58.7 (7)	C18—C19—C20—C15	−0.4 (9)
N1—C4—N4—C6	−57.7 (6)	C20—C15—C21—O4	−4.7 (9)
N1—C4—N4—C5	58.7 (7)	C16—C15—C21—O4	173.6 (6)
C12—C7—C8—C9	−1.0 (9)	C20—C15—C21—O3	174.8 (5)
C13—C7—C8—C9	−177.7 (5)	C16—C15—C21—O3	−6.9 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.83	2.654 (6)	166
O3—H3···N2	0.84	1.8	2.620 (6)	164
C1—H1A···O2	0.99	2.63	3.276 (7)	123
C2—H2A···O2^i	0.99	2.61	3.239 (8)	121
C3—H3B···N4^ii	0.99	2.74	3.684 (8)	160
C4—H4B···O2	0.99	2.69	3.327 (8)	123
C5—H5B···N3^iii	0.99	2.92	3.885 (9)	164

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x+1, y, z; (iii) x−1/2, −y+1/2, z−1/2.

(4) bis(cinnamic acid).(hexamethylenetetramine)

Crystal data

C6H12N4·2(C9H8O2)	F(000) = 928
Mr = 436.5	Dx = 1.319 Mg m^−3
Orthorhombic, Cmc21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 5707 reflections
a = 30.8030 (6) Å	θ = 2.2–28.2°
b = 9.6904 (2) Å	µ = 0.09 mm^−1
c = 7.3655 (1) Å	T = 173 K
V = 2198.55 (7) Å^3	Block, colourless
Z = 4	0.47 × 0.35 × 0.25 mm

Data collection

Bruker APEX II CCD area detector diffractometer	1376 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ω scans	θmax = 28.0°, θmin = 2.2°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −40→40
Tmin = 0.96, Tmax = 0.98	k = −12→12
10013 measured reflections	l = −9→9
1452 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0532P)^2 + 0.4277P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.006
1452 reflections	Δρmax = 0.19 e Å^−3
155 parameters	Δρmin = −0.18 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0062 (9)

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.03849 (5)	0.37265 (15)	0.2950 (2)	0.0292 (3)
H1A	0.0388	0.4682	0.3426	0.035*
H1B	0.0649	0.3599	0.22	0.035*
C2	0	0.2091 (2)	0.1149 (3)	0.0357 (5)
H2A	−0.026	0.194	0.0384	0.043*	0.5
H2B	0.026	0.194	0.0384	0.043*	0.5
C3	0.03864 (5)	0.13185 (14)	0.3752 (2)	0.0293 (3)
H3A	0.0649	0.1157	0.3008	0.035*
H3B	0.0389	0.0652	0.4771	0.035*
C4	0	0.2947 (2)	0.5582 (3)	0.0278 (4)
H4A	0	0.389	0.6099	0.033*
H4B	0	0.2282	0.6603	0.033*
N1	0.03962 (4)	0.27488 (12)	0.4487 (2)	0.0263 (3)
N2	0	0.35338 (19)	0.1812 (3)	0.0297 (4)
N3	0	0.10861 (17)	0.2640 (3)	0.0295 (4)
C5	0.16747 (5)	0.23858 (15)	1.2599 (2)	0.0270 (3)
C6	0.18749 (5)	0.36705 (16)	1.2851 (3)	0.0317 (3)
H6	0.1828	0.4389	1.1995	0.038*
C7	0.21396 (5)	0.38995 (18)	1.4338 (3)	0.0370 (4)
H7	0.2279	0.4767	1.4482	0.044*
C8	0.22027 (5)	0.2873 (2)	1.5617 (2)	0.0387 (4)
H8	0.2386	0.3032	1.6633	0.046*
C9	0.19968 (6)	0.16122 (18)	1.5406 (3)	0.0390 (4)
H9	0.2034	0.0912	1.6295	0.047*
C10	0.17361 (5)	0.13669 (17)	1.3908 (2)	0.0328 (4)
H10	0.1598	0.0496	1.3772	0.039*
C11	0.14194 (5)	0.20681 (15)	1.0972 (2)	0.0279 (3)
H11	0.129	0.1179	1.0921	0.034*
C12	0.13503 (5)	0.28929 (16)	0.9564 (2)	0.0304 (3)
H12	0.1475	0.3789	0.9557	0.036*
C13	0.10827 (5)	0.24456 (15)	0.8007 (2)	0.0290 (3)
O1	0.10152 (4)	0.34384 (12)	0.68137 (19)	0.0359 (3)
H1	0.0824 (7)	0.313 (2)	0.589 (4)	0.054*
O2	0.09381 (5)	0.12883 (13)	0.7843 (2)	0.0473 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0291 (7)	0.0213 (6)	0.0370 (9)	−0.0027 (5)	0.0037 (7)	0.0038 (6)
C2	0.0498 (14)	0.0320 (11)	0.0253 (10)	0	0	−0.0030 (10)
C3	0.0314 (7)	0.0186 (6)	0.0379 (9)	0.0041 (5)	0.0002 (6)	−0.0007 (6)
C4	0.0347 (11)	0.0240 (9)	0.0248 (10)	0	0	−0.0031 (8)
N1	0.0267 (6)	0.0201 (5)	0.0323 (6)	0.0003 (4)	−0.0036 (5)	−0.0008 (5)
N2	0.0387 (10)	0.0230 (8)	0.0274 (9)	0	0	0.0048 (7)
N3	0.0371 (9)	0.0211 (8)	0.0303 (10)	0	0	−0.0040 (7)
C5	0.0253 (7)	0.0264 (7)	0.0294 (8)	0.0021 (5)	0.0049 (6)	−0.0019 (6)
C6	0.0366 (8)	0.0277 (7)	0.0307 (8)	−0.0012 (6)	0.0029 (7)	−0.0012 (7)
C7	0.0370 (8)	0.0368 (8)	0.0374 (9)	−0.0039 (7)	0.0007 (7)	−0.0095 (8)
C8	0.0336 (8)	0.0483 (9)	0.0340 (9)	0.0092 (7)	−0.0054 (7)	−0.0074 (8)
C9	0.0447 (9)	0.0389 (8)	0.0334 (8)	0.0119 (7)	−0.0014 (8)	0.0038 (8)
C10	0.0355 (8)	0.0297 (7)	0.0332 (9)	0.0017 (6)	0.0039 (7)	0.0016 (7)
C11	0.0264 (7)	0.0261 (7)	0.0313 (7)	−0.0014 (5)	0.0047 (6)	−0.0033 (6)
C12	0.0280 (7)	0.0277 (7)	0.0353 (8)	−0.0050 (5)	−0.0018 (6)	−0.0017 (6)
C13	0.0261 (7)	0.0274 (7)	0.0334 (8)	−0.0011 (5)	−0.0012 (6)	−0.0002 (7)
O1	0.0393 (6)	0.0274 (5)	0.0409 (7)	−0.0023 (5)	−0.0136 (6)	0.0015 (5)
O2	0.0612 (8)	0.0330 (6)	0.0477 (8)	−0.0187 (6)	−0.0175 (8)	0.0063 (6)

Geometric parameters (Å, º)

C1—N2	1.464 (2)	C5—C6	1.402 (2)
C1—N1	1.476 (2)	C5—C11	1.466 (2)
C1—H1A	0.99	C6—C7	1.383 (3)
C1—H1B	0.99	C6—H6	0.95
C2—N3	1.468 (3)	C7—C8	1.384 (3)
C2—N2	1.481 (3)	C7—H7	0.95
C2—H2A	0.99	C8—C9	1.385 (3)
C2—H2B	0.99	C8—H8	0.95
C3—N3	1.4623 (19)	C9—C10	1.385 (3)
C3—N1	1.4883 (18)	C9—H9	0.95
C3—H3A	0.99	C10—H10	0.95
C3—H3B	0.99	C11—C12	1.327 (2)
C4—N1	1.4757 (18)	C11—H11	0.95
C4—N1^i	1.4757 (18)	C12—C13	1.477 (2)
C4—H4A	0.99	C12—H12	0.95
C4—H4B	0.99	C13—O2	1.2126 (18)
N2—C1^i	1.464 (2)	C13—O1	1.320 (2)
N3—C3^i	1.4623 (19)	O1—H1	0.95 (3)
C5—C10	1.393 (2)
N2—C1—N1	112.10 (12)	C3—N3—C2	108.47 (11)
N2—C1—H1A	109.2	C3^i—N3—C2	108.47 (11)
N1—C1—H1A	109.2	C10—C5—C6	118.57 (16)
N2—C1—H1B	109.2	C10—C5—C11	119.32 (14)
N1—C1—H1B	109.2	C6—C5—C11	122.05 (15)
H1A—C1—H1B	107.9	C7—C6—C5	120.44 (17)
N3—C2—N2	112.34 (19)	C7—C6—H6	119.8
N3—C2—H2A	109.1	C5—C6—H6	119.8
N2—C2—H2A	109.1	C6—C7—C8	120.43 (16)
N3—C2—H2B	109.1	C6—C7—H7	119.8
N2—C2—H2B	109.1	C8—C7—H7	119.8
H2A—C2—H2B	107.9	C7—C8—C9	119.56 (17)
N3—C3—N1	111.32 (12)	C7—C8—H8	120.2
N3—C3—H3A	109.4	C9—C8—H8	120.2
N1—C3—H3A	109.4	C10—C9—C8	120.40 (17)
N3—C3—H3B	109.4	C10—C9—H9	119.8
N1—C3—H3B	109.4	C8—C9—H9	119.8
H3A—C3—H3B	108	C9—C10—C5	120.56 (15)
N1—C4—N1^i	111.60 (18)	C9—C10—H10	119.7
N1—C4—H4A	109.3	C5—C10—H10	119.7
N1^i—C4—H4A	109.3	C12—C11—C5	126.77 (13)
N1—C4—H4B	109.3	C12—C11—H11	116.6
N1^i—C4—H4B	109.3	C5—C11—H11	116.6
H4A—C4—H4B	108	C11—C12—C13	121.31 (13)
C4—N1—C1	108.42 (13)	C11—C12—H12	119.3
C4—N1—C3	107.66 (12)	C13—C12—H12	119.3
C1—N1—C3	108.58 (13)	O2—C13—O1	123.36 (16)
C1—N2—C1^i	108.14 (19)	O2—C13—C12	123.62 (16)
C1—N2—C2	108.01 (11)	O1—C13—C12	113.02 (13)
C1^i—N2—C2	108.01 (11)	C13—O1—H1	110.1 (14)
C3—N3—C3^i	108.98 (18)
N1^i—C4—N1—C1	57.70 (19)	C10—C5—C6—C7	2.2 (2)
N1^i—C4—N1—C3	−59.6 (2)	C11—C5—C6—C7	−175.18 (15)
N2—C1—N1—C4	−58.53 (17)	C5—C6—C7—C8	−1.4 (3)
N2—C1—N1—C3	58.16 (16)	C6—C7—C8—C9	−0.4 (3)
N3—C3—N1—C4	59.00 (18)	C7—C8—C9—C10	1.3 (3)
N3—C3—N1—C1	−58.19 (17)	C8—C9—C10—C5	−0.5 (3)
N1—C1—N2—C1^i	58.87 (19)	C6—C5—C10—C9	−1.3 (2)
N1—C1—N2—C2	−57.78 (18)	C11—C5—C10—C9	176.20 (15)
N3—C2—N2—C1	58.37 (12)	C10—C5—C11—C12	−176.18 (15)
N3—C2—N2—C1^i	−58.37 (12)	C6—C5—C11—C12	1.2 (2)
N1—C3—N3—C3^i	−59.4 (2)	C5—C11—C12—C13	−179.59 (14)
N1—C3—N3—C2	58.54 (18)	C11—C12—C13—O2	−5.7 (3)
N2—C2—N3—C3	−59.12 (11)	C11—C12—C13—O1	174.05 (14)
N2—C2—N3—C3^i	59.12 (11)

Symmetry code: (i) −x, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.95 (3)	1.71 (3)	2.6496 (18)	168 (2)
C3—H3B···N3^ii	0.99	2.96	3.879 (2)	155
C4—H4A···N2^iii	0.99	2.55	3.528 (3)	169

Symmetry codes: (ii) −x, −y, z+1/2; (iii) −x, −y+1, z+1/2.

(5) bis(4-nitrobenzoic acid).(hexamethylenetetramine) dihydrate

Crystal data

C6H12N4·2(C7H5NO4)·2(H2O)	F(000) = 1072
Mr = 510.47	Dx = 1.517 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6174 reflections
a = 12.0807 (4) Å	θ = 3.2–28.3°
b = 7.4730 (2) Å	µ = 0.12 mm^−1
c = 25.0633 (7) Å	T = 173 K
β = 98.909 (1)°	Block, colourless
V = 2235.39 (11) Å^3	0.37 × 0.31 × 0.09 mm
Z = 4

Data collection

Bruker APEX II CCD area detector diffractometer	2336 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 28°, θmin = 1.6°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −15→15
Tmin = 0.96, Tmax = 0.98	k = −9→9
16252 measured reflections	l = −33→32
2697 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0746P)^2 + 0.5453P] where P = (Fo^2 + 2Fc^2)/3
2697 reflections	(Δ/σ)max = 0.003
173 parameters	Δρmax = 0.33 e Å^−3
3 restraints	Δρmin = −0.28 e Å^−3

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.63894 (8)	0.20671 (14)	0.24788 (4)	0.0225 (2)
H1A	0.678	0.1312	0.2242	0.027*
H1B	0.6958	0.2821	0.2701	0.027*
C2	0.52603 (9)	0.20649 (15)	0.31804 (4)	0.0230 (2)
H2A	0.5817	0.2819	0.341	0.028*
H2B	0.4882	0.1307	0.3422	0.028*
C3	0.5	−0.0203 (2)	0.25	0.0240 (3)
H3A	0.4623	−0.0982	0.2736	0.029*	0.5
H3B	0.5377	−0.0982	0.2264	0.029*	0.5
C4	0.5	0.4335 (2)	0.25	0.0245 (3)
H4A	0.4447	0.5114	0.2278	0.029*	0.5
H4B	0.5553	0.5114	0.2722	0.029*	0.5
N1	0.55785 (7)	0.32295 (12)	0.21416 (3)	0.0220 (2)
N2	0.58459 (7)	0.09067 (12)	0.28372 (3)	0.0210 (2)
C5	0.64857 (7)	1.00770 (13)	0.04469 (4)	0.0180 (2)
C6	0.63945 (8)	0.94181 (14)	−0.00781 (4)	0.0193 (2)
H6	0.6483	0.8174	−0.0138	0.023*
C7	0.61751 (8)	1.05742 (14)	−0.05131 (4)	0.0211 (2)
H7	0.6119	1.0144	−0.0873	0.025*
C8	0.60386 (8)	1.23785 (13)	−0.04100 (4)	0.0199 (2)
C9	0.61289 (8)	1.30719 (13)	0.01042 (4)	0.0209 (2)
H9	0.6034	1.4316	0.0161	0.025*
C10	0.63624 (8)	1.19054 (13)	0.05374 (4)	0.0202 (2)
H10	0.6439	1.2351	0.0896	0.024*
C11	0.67147 (8)	0.88629 (13)	0.09262 (4)	0.0198 (2)
N3	0.57974 (7)	1.36026 (13)	−0.08743 (4)	0.0257 (2)
O1	0.66848 (7)	0.71520 (10)	0.07904 (3)	0.02437 (19)
H1	0.6819 (12)	0.6422 (19)	0.1096 (6)	0.037*
O2	0.69003 (8)	0.94056 (11)	0.13859 (3)	0.0322 (2)
O3	0.56430 (9)	1.29658 (13)	−0.13271 (4)	0.0398 (2)
O4	0.57552 (8)	1.52114 (11)	−0.07795 (4)	0.0362 (2)
O1W	0.70875 (6)	0.48453 (11)	0.15381 (3)	0.0251 (2)
H1W	0.6606 (10)	0.4486 (19)	0.1720 (5)	0.038*
H2W	0.7722 (8)	0.4976 (18)	0.1734 (5)	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0186 (5)	0.0286 (5)	0.0204 (5)	0.0000 (4)	0.0030 (4)	−0.0008 (4)
C2	0.0239 (5)	0.0300 (6)	0.0148 (5)	0.0021 (4)	0.0022 (4)	−0.0005 (4)
C3	0.0267 (7)	0.0191 (7)	0.0256 (8)	0	0.0018 (6)	0
C4	0.0275 (7)	0.0193 (7)	0.0263 (8)	0	0.0028 (6)	0
N1	0.0227 (4)	0.0246 (4)	0.0188 (4)	−0.0028 (3)	0.0030 (3)	0.0025 (3)
N2	0.0207 (4)	0.0231 (4)	0.0185 (4)	0.0024 (3)	0.0012 (3)	0.0012 (3)
C5	0.0132 (4)	0.0211 (5)	0.0200 (5)	−0.0008 (3)	0.0037 (3)	0.0000 (4)
C6	0.0162 (4)	0.0195 (5)	0.0223 (5)	−0.0005 (3)	0.0035 (4)	−0.0023 (4)
C7	0.0176 (4)	0.0257 (5)	0.0202 (5)	−0.0016 (4)	0.0033 (4)	−0.0019 (4)
C8	0.0139 (4)	0.0231 (5)	0.0227 (5)	−0.0007 (4)	0.0027 (4)	0.0046 (4)
C9	0.0171 (4)	0.0182 (5)	0.0279 (5)	−0.0011 (3)	0.0049 (4)	−0.0005 (4)
C10	0.0182 (4)	0.0220 (5)	0.0208 (5)	−0.0020 (4)	0.0046 (4)	−0.0028 (4)
C11	0.0171 (4)	0.0221 (5)	0.0208 (5)	−0.0002 (4)	0.0050 (4)	−0.0003 (4)
N3	0.0207 (4)	0.0296 (5)	0.0270 (5)	0.0008 (4)	0.0046 (4)	0.0082 (4)
O1	0.0323 (4)	0.0197 (4)	0.0210 (4)	0.0010 (3)	0.0034 (3)	0.0020 (3)
O2	0.0472 (5)	0.0293 (4)	0.0192 (4)	0.0016 (4)	0.0025 (3)	−0.0016 (3)
O3	0.0509 (6)	0.0445 (5)	0.0227 (4)	0.0026 (4)	0.0012 (4)	0.0065 (4)
O4	0.0426 (5)	0.0265 (4)	0.0405 (5)	0.0049 (4)	0.0093 (4)	0.0105 (4)
O1W	0.0249 (4)	0.0291 (4)	0.0205 (4)	−0.0069 (3)	0.0010 (3)	0.0047 (3)

Geometric parameters (Å, º)

C1—N2	1.4739 (13)	C5—C10	1.3968 (14)
C1—N1	1.4737 (13)	C5—C11	1.4967 (14)
C1—H1A	0.99	C6—C7	1.3842 (15)
C1—H1B	0.99	C6—H6	0.95
C2—N2	1.4758 (13)	C7—C8	1.3875 (15)
C2—N1^i	1.4773 (13)	C7—H7	0.95
C2—H2A	0.99	C8—C9	1.3778 (15)
C2—H2B	0.99	C8—N3	1.4734 (13)
C3—N2	1.4760 (12)	C9—C10	1.3868 (15)
C3—N2^i	1.4760 (12)	C9—H9	0.95
C3—H3A	0.99	C10—H10	0.95
C3—H3B	0.99	C11—O2	1.2092 (13)
C4—N1	1.4738 (12)	C11—O1	1.3222 (13)
C4—N1^i	1.4738 (12)	N3—O3	1.2179 (14)
C4—H4A	0.99	N3—O4	1.2281 (13)
C4—H4B	0.99	O1—H1	0.933 (15)
N1—C2^i	1.4773 (13)	O1W—H1W	0.838 (8)
C5—C6	1.3932 (14)	O1W—H2W	0.849 (9)
N2—C1—N1	112.15 (8)	C1—N2—C2	108.01 (8)
N2—C1—H1A	109.2	C3—N2—C2	108.13 (7)
N1—C1—H1A	109.2	C6—C5—C10	120.29 (9)
N2—C1—H1B	109.2	C6—C5—C11	121.44 (9)
N1—C1—H1B	109.2	C10—C5—C11	118.28 (9)
H1A—C1—H1B	107.9	C7—C6—C5	120.05 (9)
N2—C2—N1^i	112.16 (8)	C7—C6—H6	120
N2—C2—H2A	109.2	C5—C6—H6	120
N1^i—C2—H2A	109.2	C6—C7—C8	118.27 (10)
N2—C2—H2B	109.2	C6—C7—H7	120.9
N1^i—C2—H2B	109.2	C8—C7—H7	120.9
H2A—C2—H2B	107.9	C9—C8—C7	123.04 (10)
N2—C3—N2^i	111.64 (12)	C9—C8—N3	118.86 (9)
N2—C3—H3A	109.3	C7—C8—N3	118.09 (9)
N2^i—C3—H3A	109.3	C8—C9—C10	118.23 (9)
N2—C3—H3B	109.3	C8—C9—H9	120.9
N2^i—C3—H3B	109.3	C10—C9—H9	120.9
H3A—C3—H3B	108	C9—C10—C5	120.11 (10)
N1—C4—N1^i	111.82 (12)	C9—C10—H10	119.9
N1—C4—H4A	109.3	C5—C10—H10	119.9
N1^i—C4—H4A	109.3	O2—C11—O1	124.28 (10)
N1—C4—H4B	109.3	O2—C11—C5	123.06 (9)
N1^i—C4—H4B	109.3	O1—C11—C5	112.66 (9)
H4A—C4—H4B	107.9	O3—N3—O4	123.91 (10)
C4—N1—C1	108.47 (7)	O3—N3—C8	118.45 (9)
C4—N1—C2^i	108.26 (7)	O4—N3—C8	117.64 (9)
C1—N1—C2^i	107.75 (8)	C11—O1—H1	111.1 (9)
C1—N2—C3	108.41 (7)	H1W—O1W—H2W	111.3 (13)
N1^i—C4—N1—C1	−58.38 (6)	C6—C7—C8—N3	−179.59 (8)
N1^i—C4—N1—C2^i	58.28 (6)	C7—C8—C9—C10	−0.29 (15)
N2—C1—N1—C4	58.50 (10)	N3—C8—C9—C10	−179.64 (8)
N2—C1—N1—C2^i	−58.48 (10)	C8—C9—C10—C5	−0.81 (14)
N1—C1—N2—C3	58.74 (11)	C6—C5—C10—C9	1.12 (14)
N1—C1—N2—C2	−58.21 (10)	C11—C5—C10—C9	−178.80 (8)
N2^i—C3—N2—C1	−58.43 (6)	C6—C5—C11—O2	173.01 (10)
N2^i—C3—N2—C2	58.43 (6)	C10—C5—C11—O2	−7.06 (15)
N1^i—C2—N2—C1	58.24 (11)	C6—C5—C11—O1	−7.34 (13)
N1^i—C2—N2—C3	−58.89 (11)	C10—C5—C11—O1	172.59 (8)
C10—C5—C6—C7	−0.33 (14)	C9—C8—N3—O3	−175.05 (10)
C11—C5—C6—C7	179.59 (8)	C7—C8—N3—O3	5.57 (14)
C5—C6—C7—C8	−0.73 (14)	C9—C8—N3—O4	4.34 (13)
C6—C7—C8—C9	1.06 (15)	C7—C8—N3—O4	−175.04 (9)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1W	0.933 (15)	1.616 (15)	2.5373 (11)	168 (1)
O1W—H1W···N1	0.84 (1)	1.99 (1)	2.8148 (11)	170 (1)
O1W—H2W···N2^ii	0.85 (1)	2.01 (1)	2.8465 (11)	166 (1)
C1—H1A···O2^iii	0.99	2.6	3.5162 (13)	154
C2—H2B···O2^iv	0.99	2.69	3.5809 (14)	151
C2—H2A···O4^v	0.99	2.52	3.2883 (14)	134
C9—H9···O1^vi	0.95	2.69	3.5139 (13)	146
C10—H10···O1W^vi	0.95	2.51	3.3474 (13)	147

Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y−1, z; (iv) −x+1, y−1, −z+1/2; (v) x, −y+2, z+1/2; (vi) x, y+1, z.

(6) (cis-cyclohexane-1,4-dicarboxylic acid).(hexamethylenetetramine)

Crystal data

C8H12O4·C6H12N4	F(000) = 336
Mr = 312.37	Dx = 1.394 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 4457 reflections
a = 5.9169 (4) Å	θ = 3.5–28.2°
b = 21.6383 (15) Å	µ = 0.10 mm^−1
c = 6.1135 (4) Å	T = 173 K
β = 108.028 (1)°	Block, colourless
V = 744.29 (9) Å^3	0.66 × 0.42 × 0.11 mm
Z = 2

Data collection

Bruker APEX II CCD area detector diffractometer	1671 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 28°, θmin = 1.9°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −7→7
Tmin = 0.93, Tmax = 0.98	k = −28→28
7732 measured reflections	l = −8→8
1834 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 0.2047P] where P = (Fo^2 + 2Fc^2)/3
1834 reflections	(Δ/σ)max < 0.001
109 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.0028 (2)	0.30493 (5)	0.4874 (2)	0.0255 (2)
H1A	0.0134	0.3054	0.6522	0.031*
H1B	−0.0849	0.3423	0.4147	0.031*
C2	−0.1383 (3)	0.25	0.1349 (3)	0.0301 (4)
H2A	−0.2268	0.213	0.0587	0.036*	0.5
H2B	−0.2268	0.287	0.0587	0.036*	0.5
C3	0.2259 (2)	0.30464 (5)	0.2190 (2)	0.0278 (3)
H3A	0.1422	0.3422	0.1426	0.033*
H3B	0.3874	0.3048	0.2029	0.033*
C4	0.3699 (3)	0.25	0.5758 (3)	0.0285 (3)
H4A	0.5332	0.25	0.5646	0.034*
H4B	0.3818	0.25	0.7409	0.034*
N1	0.24521 (16)	0.30643 (4)	0.46634 (16)	0.0238 (2)
N2	−0.1276 (2)	0.25	0.3783 (2)	0.0246 (3)
N3	0.0980 (3)	0.25	0.1048 (2)	0.0264 (3)
C5	0.76810 (17)	0.47070 (4)	0.88665 (17)	0.0191 (2)
H5	0.6764	0.5083	0.8158	0.023*
C6	0.97720 (19)	0.46367 (5)	0.79008 (17)	0.0213 (2)
H6A	1.0675	0.4257	0.8529	0.026*
H6B	0.9162	0.4596	0.6206	0.026*
C7	0.85884 (18)	0.48038 (5)	1.14611 (18)	0.0211 (2)
H7A	0.946	0.443	1.2204	0.025*
H7B	0.722	0.4863	1.2048	0.025*
C8	0.60253 (19)	0.41565 (5)	0.82252 (19)	0.0225 (2)
O1	0.50330 (19)	0.40969 (5)	0.59859 (15)	0.0403 (3)
H1	0.413 (3)	0.3753 (10)	0.565 (3)	0.06*
O2	0.56245 (17)	0.38095 (4)	0.96001 (16)	0.0370 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0293 (5)	0.0191 (5)	0.0317 (6)	0.0011 (4)	0.0148 (5)	−0.0038 (4)
C2	0.0244 (8)	0.0298 (8)	0.0272 (8)	0	−0.0048 (6)	0
C3	0.0362 (6)	0.0247 (5)	0.0261 (5)	−0.0056 (4)	0.0148 (5)	0.0028 (4)
C4	0.0200 (7)	0.0373 (9)	0.0238 (7)	0	0.0001 (6)	0
N1	0.0246 (5)	0.0233 (4)	0.0233 (5)	−0.0075 (3)	0.0073 (4)	−0.0046 (3)
N2	0.0176 (6)	0.0218 (6)	0.0348 (7)	0	0.0087 (5)	0
N3	0.0361 (7)	0.0246 (6)	0.0177 (6)	0	0.0075 (5)	0
C5	0.0196 (5)	0.0167 (4)	0.0208 (5)	−0.0031 (4)	0.0058 (4)	−0.0007 (4)
C6	0.0250 (5)	0.0208 (5)	0.0197 (5)	−0.0043 (4)	0.0094 (4)	−0.0039 (4)
C7	0.0233 (5)	0.0215 (5)	0.0210 (5)	−0.0041 (4)	0.0103 (4)	−0.0016 (4)
C8	0.0209 (5)	0.0182 (5)	0.0279 (5)	−0.0027 (4)	0.0068 (4)	−0.0015 (4)
O1	0.0519 (6)	0.0368 (5)	0.0274 (5)	−0.0269 (4)	0.0053 (4)	−0.0053 (4)
O2	0.0432 (5)	0.0310 (5)	0.0348 (5)	−0.0161 (4)	0.0092 (4)	0.0053 (4)

Geometric parameters (Å, º)

C1—N2	1.4610 (13)	N2—C1^i	1.4610 (13)
C1—N1	1.4794 (14)	N3—C3^i	1.4597 (14)
C1—H1A	0.99	C5—C8	1.5148 (13)
C1—H1B	0.99	C5—C7	1.5235 (14)
C2—N3	1.466 (2)	C5—C6	1.5345 (14)
C2—N2	1.470 (2)	C5—H5	1
C2—H2A	0.99	C6—C7^ii	1.5247 (14)
C2—H2B	0.99	C6—H6A	0.99
C3—N3	1.4597 (14)	C6—H6B	0.99
C3—N1	1.4816 (14)	C7—C6^ii	1.5247 (14)
C3—H3A	0.99	C7—H7A	0.99
C3—H3B	0.99	C7—H7B	0.99
C4—N1^i	1.4757 (13)	C8—O2	1.2041 (14)
C4—N1	1.4757 (13)	C8—O1	1.3183 (14)
C4—H4A	0.99	O1—H1	0.90 (2)
C4—H4B	0.99
N2—C1—N1	111.55 (9)	C1—N2—C2	108.28 (8)
N2—C1—H1A	109.3	C1^i—N2—C2	108.28 (8)
N1—C1—H1A	109.3	C3—N3—C3^i	108.18 (13)
N2—C1—H1B	109.3	C3—N3—C2	108.29 (8)
N1—C1—H1B	109.3	C3^i—N3—C2	108.29 (8)
H1A—C1—H1B	108	C8—C5—C7	111.65 (8)
N3—C2—N2	112.51 (12)	C8—C5—C6	110.88 (8)
N3—C2—H2A	109.1	C7—C5—C6	110.36 (8)
N2—C2—H2A	109.1	C8—C5—H5	107.9
N3—C2—H2B	109.1	C7—C5—H5	107.9
N2—C2—H2B	109.1	C6—C5—H5	107.9
H2A—C2—H2B	107.8	C7^ii—C6—C5	110.35 (8)
N3—C3—N1	111.96 (9)	C7^ii—C6—H6A	109.6
N3—C3—H3A	109.2	C5—C6—H6A	109.6
N1—C3—H3A	109.2	C7^ii—C6—H6B	109.6
N3—C3—H3B	109.2	C5—C6—H6B	109.6
N1—C3—H3B	109.2	H6A—C6—H6B	108.1
H3A—C3—H3B	107.9	C5—C7—C6^ii	111.53 (8)
N1^i—C4—N1	111.69 (12)	C5—C7—H7A	109.3
N1^i—C4—H4A	109.3	C6^ii—C7—H7A	109.3
N1—C4—H4A	109.3	C5—C7—H7B	109.3
N1^i—C4—H4B	109.3	C6^ii—C7—H7B	109.3
N1—C4—H4B	109.3	H7A—C7—H7B	108
H4A—C4—H4B	107.9	O2—C8—O1	122.91 (10)
C4—N1—C1	107.71 (9)	O2—C8—C5	124.13 (10)
C4—N1—C3	108.12 (10)	O1—C8—C5	112.96 (9)
C1—N1—C3	108.54 (9)	C8—O1—H1	111.0 (12)
C1—N2—C1^i	108.87 (12)
N1^i—C4—N1—C1	59.21 (15)	N1—C3—N3—C2	57.73 (13)
N1^i—C4—N1—C3	−57.90 (15)	N2—C2—N3—C3	−58.54 (8)
N2—C1—N1—C4	−58.83 (12)	N2—C2—N3—C3^i	58.54 (8)
N2—C1—N1—C3	58.00 (12)	C8—C5—C6—C7^ii	179.47 (8)
N3—C3—N1—C4	58.75 (12)	C7—C5—C6—C7^ii	−56.29 (12)
N3—C3—N1—C1	−57.82 (12)	C8—C5—C7—C6^ii	−179.24 (9)
N1—C1—N2—C1^i	59.23 (15)	C6—C5—C7—C6^ii	56.97 (12)
N1—C1—N2—C2	−58.30 (12)	C7—C5—C8—O2	−5.50 (15)
N3—C2—N2—C1	58.95 (8)	C6—C5—C8—O2	118.01 (12)
N3—C2—N2—C1^i	−58.95 (8)	C7—C5—C8—O1	173.85 (9)
N1—C3—N3—C3^i	−59.43 (15)	C6—C5—C8—O1	−62.65 (12)

Symmetry codes: (i) x, −y+1/2, z; (ii) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.90 (2)	1.79 (2)	2.6859 (12)	173 (2)
C1—H1A···N3^iii	0.99	2.91	3.8288 (17)	154
C2—H2A···O2^iv	0.99	2.36	3.3368 (13)	167
C4—H4A···N2^v	0.99	2.6	3.539 (2)	159

Symmetry codes: (iii) x, y, z+1; (iv) x−1, −y+1/2, z−1; (v) x+1, y, z.

(7) (trans-cyclohexane-1,4-dicarboxylic acid).(hexamethylenetetramine)

Crystal data

C8H12O4·C6H12N4	F(000) = 2688
Mr = 312.37	Dx = 1.343 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 6141 reflections
a = 23.7999 (4) Å	θ = 2.5–28.1°
b = 44.9245 (8) Å	µ = 0.1 mm^−1
c = 5.7804 (1) Å	T = 173 K
V = 6180.40 (19) Å^3	Block, colourless
Z = 16	0.36 × 0.31 × 0.12 mm

Data collection

Bruker APEX II CCD area detector diffractometer	1915 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 28°, θmin = 1.8°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −31→31
Tmin = 0.96, Tmax = 0.98	k = −58→57
18095 measured reflections	l = −7→7
2054 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.076P)^2] where P = (Fo^2 + 2Fc^2)/3
2054 reflections	(Δ/σ)max = 0.001
205 parameters	Δρmax = 0.22 e Å^−3
1 restraint	Δρmin = −0.21 e Å^−3

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.53416 (7)	0.62045 (3)	0.5071 (3)	0.0257 (3)
H1A	0.5743	0.6182	0.5485	0.031*
H1B	0.5312	0.6201	0.3363	0.031*
C2	0.51857 (8)	0.64894 (4)	0.8495 (3)	0.0299 (4)
H2A	0.5587	0.6469	0.8916	0.036*
H2B	0.5048	0.6681	0.9126	0.036*
C3	0.50758 (8)	0.59627 (4)	0.8583 (3)	0.0289 (4)
H3A	0.4862	0.5796	0.9272	0.035*
H3B	0.5476	0.5938	0.9009	0.035*
C4	0.44194 (7)	0.59917 (4)	0.5459 (3)	0.0286 (4)
H4A	0.4374	0.5986	0.3757	0.034*
H4B	0.4201	0.5825	0.6123	0.034*
C5	0.45262 (7)	0.65156 (3)	0.5350 (3)	0.0277 (4)
H5A	0.4378	0.6708	0.5922	0.033*
H5B	0.4484	0.6513	0.3646	0.033*
C6	0.42742 (8)	0.62778 (4)	0.8871 (3)	0.0298 (4)
H6A	0.4129	0.6468	0.9496	0.036*
H6B	0.4054	0.6114	0.957	0.036*
N1	0.50203 (6)	0.59523 (3)	0.6042 (3)	0.0242 (3)
N2	0.51316 (6)	0.64924 (3)	0.5949 (3)	0.0254 (3)
N3	0.48677 (7)	0.62448 (3)	0.9529 (3)	0.0280 (3)
N4	0.41966 (6)	0.62737 (3)	0.6342 (3)	0.0260 (3)
C7	0.61319 (6)	0.53201 (3)	0.1126 (3)	0.0237 (3)
H7	0.6156	0.5464	−0.0191	0.028*
C8	0.57384 (7)	0.50700 (4)	0.0359 (4)	0.0292 (4)
H8A	0.5689	0.4927	0.1649	0.035*
H8B	0.5365	0.5155	−0.0015	0.035*
C9	0.59657 (8)	0.49049 (4)	−0.1754 (4)	0.0353 (4)
H9A	0.5956	0.5039	−0.3109	0.042*
H9B	0.572	0.4733	−0.2092	0.042*
C10	0.65677 (8)	0.47949 (4)	−0.1394 (3)	0.0306 (4)
H10	0.6708	0.4725	−0.2931	0.037*
C11	0.69497 (7)	0.50511 (4)	−0.0633 (4)	0.0345 (4)
H11A	0.7332	0.4973	−0.0325	0.041*
H11B	0.6977	0.5199	−0.1898	0.041*
C12	0.67255 (6)	0.52025 (3)	0.1535 (4)	0.0284 (4)
H12A	0.6976	0.5369	0.1966	0.034*
H12B	0.6721	0.5058	0.2831	0.034*
C13	0.59170 (7)	0.54924 (3)	0.3187 (3)	0.0258 (3)
C14	0.65949 (7)	0.45302 (3)	0.0241 (3)	0.0278 (4)
O1	0.53651 (5)	0.55122 (3)	0.3272 (3)	0.0367 (3)
H1	0.5248 (11)	0.5632 (6)	0.420 (7)	0.055*
O2	0.62180 (6)	0.56089 (3)	0.4612 (3)	0.0485 (4)
O3	0.71021 (6)	0.44761 (3)	0.0977 (4)	0.0491 (4)
H3	0.7109 (11)	0.4319 (7)	0.166 (7)	0.074*
O4	0.61995 (6)	0.43793 (3)	0.0754 (4)	0.0564 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0257 (7)	0.0296 (8)	0.0216 (8)	0.0027 (6)	0.0036 (7)	0.0003 (6)
C2	0.0319 (8)	0.0302 (8)	0.0277 (9)	0.0005 (6)	−0.0055 (7)	−0.0066 (7)
C3	0.0352 (9)	0.0280 (8)	0.0234 (8)	0.0079 (6)	−0.0015 (7)	0.0059 (7)
C4	0.0295 (8)	0.0277 (7)	0.0286 (9)	−0.0021 (6)	−0.0031 (7)	−0.0067 (7)
C5	0.0280 (8)	0.0260 (7)	0.0291 (9)	0.0056 (6)	−0.0030 (7)	0.0057 (7)
C6	0.0283 (8)	0.0349 (8)	0.0264 (9)	0.0031 (6)	0.0067 (7)	−0.0019 (7)
N1	0.0289 (7)	0.0232 (6)	0.0206 (6)	0.0046 (5)	0.0012 (5)	−0.0010 (5)
N2	0.0265 (7)	0.0236 (6)	0.0263 (7)	0.0010 (5)	−0.0001 (6)	0.0018 (6)
N3	0.0338 (7)	0.0320 (7)	0.0183 (7)	0.0050 (5)	−0.0024 (6)	−0.0017 (5)
N4	0.0218 (6)	0.0312 (7)	0.0250 (8)	0.0035 (5)	−0.0010 (6)	0.0001 (6)
C7	0.0204 (7)	0.0195 (6)	0.0313 (8)	0.0002 (5)	−0.0011 (6)	0.0020 (6)
C8	0.0218 (7)	0.0265 (7)	0.0392 (10)	0.0001 (6)	−0.0013 (7)	−0.0077 (7)
C9	0.0422 (10)	0.0320 (8)	0.0318 (10)	0.0094 (7)	−0.0085 (8)	−0.0059 (8)
C10	0.0394 (9)	0.0270 (7)	0.0253 (8)	0.0091 (7)	0.0057 (8)	0.0006 (7)
C11	0.0297 (8)	0.0252 (7)	0.0487 (12)	0.0041 (6)	0.0140 (8)	0.0093 (7)
C12	0.0189 (7)	0.0209 (7)	0.0455 (10)	−0.0013 (5)	−0.0011 (7)	0.0030 (7)
C13	0.0275 (7)	0.0186 (6)	0.0314 (9)	−0.0012 (5)	−0.0038 (7)	−0.0001 (6)
C14	0.0332 (8)	0.0207 (7)	0.0295 (9)	0.0019 (6)	0.0023 (7)	−0.0027 (6)
O1	0.0280 (6)	0.0378 (6)	0.0443 (9)	0.0066 (5)	0.0013 (6)	−0.0177 (6)
O2	0.0387 (7)	0.0544 (9)	0.0523 (10)	−0.0009 (6)	−0.0098 (7)	−0.0248 (8)
O3	0.0347 (7)	0.0361 (7)	0.0766 (12)	0.0004 (5)	−0.0063 (8)	0.0273 (8)
O4	0.0435 (8)	0.0427 (8)	0.0832 (14)	−0.0127 (6)	−0.0104 (9)	0.0211 (9)

Geometric parameters (Å, º)

C1—N2	1.477 (2)	C7—C13	1.510 (2)
C1—N1	1.478 (2)	C7—C12	1.527 (2)
C1—H1A	0.99	C7—C8	1.529 (2)
C1—H1B	0.99	C7—H7	1
C2—N3	1.462 (2)	C8—C9	1.527 (3)
C2—N2	1.477 (2)	C8—H8A	0.99
C2—H2A	0.99	C8—H8B	0.99
C2—H2B	0.99	C9—C10	1.530 (2)
C3—N3	1.466 (2)	C9—H9A	0.99
C3—N1	1.475 (2)	C9—H9B	0.99
C3—H3A	0.99	C10—C14	1.520 (2)
C3—H3B	0.99	C10—C11	1.531 (3)
C4—N4	1.465 (2)	C10—H10	1
C4—N1	1.480 (2)	C11—C12	1.522 (3)
C4—H4A	0.99	C11—H11A	0.99
C4—H4B	0.99	C11—H11B	0.99
C5—N4	1.458 (2)	C12—H12A	0.99
C5—N2	1.485 (2)	C12—H12B	0.99
C5—H5A	0.99	C13—O2	1.211 (2)
C5—H5B	0.99	C13—O1	1.3173 (19)
C6—N3	1.470 (2)	C14—O4	1.197 (2)
C6—N4	1.474 (2)	C14—O3	1.303 (2)
C6—H6A	0.99	O1—H1	0.81 (4)
C6—H6B	0.99	O3—H3	0.81 (3)
N2—C1—N1	111.47 (13)	C5—N4—C6	108.27 (15)
N2—C1—H1A	109.3	C4—N4—C6	108.12 (14)
N1—C1—H1A	109.3	C13—C7—C12	111.63 (14)
N2—C1—H1B	109.3	C13—C7—C8	113.46 (13)
N1—C1—H1B	109.3	C12—C7—C8	110.93 (12)
H1A—C1—H1B	108	C13—C7—H7	106.8
N3—C2—N2	111.66 (14)	C12—C7—H7	106.8
N3—C2—H2A	109.3	C8—C7—H7	106.8
N2—C2—H2A	109.3	C9—C8—C7	111.82 (15)
N3—C2—H2B	109.3	C9—C8—H8A	109.3
N2—C2—H2B	109.3	C7—C8—H8A	109.3
H2A—C2—H2B	107.9	C9—C8—H8B	109.3
N3—C3—N1	111.62 (13)	C7—C8—H8B	109.3
N3—C3—H3A	109.3	H8A—C8—H8B	107.9
N1—C3—H3A	109.3	C8—C9—C10	112.32 (15)
N3—C3—H3B	109.3	C8—C9—H9A	109.1
N1—C3—H3B	109.3	C10—C9—H9A	109.1
H3A—C3—H3B	108	C8—C9—H9B	109.1
N4—C4—N1	111.94 (13)	C10—C9—H9B	109.1
N4—C4—H4A	109.2	H9A—C9—H9B	107.9
N1—C4—H4A	109.2	C14—C10—C9	112.17 (15)
N4—C4—H4B	109.2	C14—C10—C11	112.59 (16)
N1—C4—H4B	109.2	C9—C10—C11	110.62 (14)
H4A—C4—H4B	107.9	C14—C10—H10	107
N4—C5—N2	112.21 (13)	C9—C10—H10	107
N4—C5—H5A	109.2	C11—C10—H10	107
N2—C5—H5A	109.2	C12—C11—C10	111.35 (14)
N4—C5—H5B	109.2	C12—C11—H11A	109.4
N2—C5—H5B	109.2	C10—C11—H11A	109.4
H5A—C5—H5B	107.9	C12—C11—H11B	109.4
N3—C6—N4	112.06 (15)	C10—C11—H11B	109.4
N3—C6—H6A	109.2	H11A—C11—H11B	108
N4—C6—H6A	109.2	C11—C12—C7	110.58 (16)
N3—C6—H6B	109.2	C11—C12—H12A	109.5
N4—C6—H6B	109.2	C7—C12—H12A	109.5
H6A—C6—H6B	107.9	C11—C12—H12B	109.5
C3—N1—C1	107.91 (14)	C7—C12—H12B	109.5
C3—N1—C4	108.03 (14)	H12A—C12—H12B	108.1
C1—N1—C4	108.77 (13)	O2—C13—O1	122.35 (17)
C1—N2—C2	107.73 (13)	O2—C13—C7	123.92 (15)
C1—N2—C5	108.05 (13)	O1—C13—C7	113.70 (14)
C2—N2—C5	108.50 (15)	O4—C14—O3	122.80 (18)
C2—N3—C3	108.79 (14)	O4—C14—C10	124.29 (18)
C2—N3—C6	108.41 (14)	O3—C14—C10	112.87 (15)
C3—N3—C6	108.37 (14)	C13—O1—H1	114.4 (19)
C5—N4—C4	108.24 (14)	C14—O3—H3	110 (2)
N3—C3—N1—C1	58.71 (18)	N1—C4—N4—C6	−58.42 (19)
N3—C3—N1—C4	−58.74 (18)	N3—C6—N4—C5	−58.65 (17)
N2—C1—N1—C3	−59.30 (18)	N3—C6—N4—C4	58.40 (18)
N2—C1—N1—C4	57.66 (17)	C13—C7—C8—C9	178.99 (14)
N4—C4—N1—C3	58.76 (18)	C12—C7—C8—C9	−54.4 (2)
N4—C4—N1—C1	−58.12 (18)	C7—C8—C9—C10	53.0 (2)
N1—C1—N2—C2	59.35 (18)	C8—C9—C10—C14	73.3 (2)
N1—C1—N2—C5	−57.69 (18)	C8—C9—C10—C11	−53.3 (2)
N3—C2—N2—C1	−59.07 (18)	C14—C10—C11—C12	−70.49 (18)
N3—C2—N2—C5	57.67 (17)	C9—C10—C11—C12	55.9 (2)
N4—C5—N2—C1	59.04 (18)	C10—C11—C12—C7	−58.04 (18)
N4—C5—N2—C2	−57.50 (17)	C13—C7—C12—C11	−175.53 (13)
N2—C2—N3—C3	59.02 (19)	C8—C7—C12—C11	56.87 (19)
N2—C2—N3—C6	−58.64 (19)	C12—C7—C13—O2	23.2 (2)
N1—C3—N3—C2	−58.8 (2)	C8—C7—C13—O2	149.44 (17)
N1—C3—N3—C6	58.85 (19)	C12—C7—C13—O1	−158.51 (14)
N4—C6—N3—C2	59.22 (18)	C8—C7—C13—O1	−32.3 (2)
N4—C6—N3—C3	−58.71 (18)	C9—C10—C14—O4	16.9 (3)
N2—C5—N4—C4	−59.31 (19)	C11—C10—C14—O4	142.5 (2)
N2—C5—N4—C6	57.66 (18)	C9—C10—C14—O3	−165.42 (17)
N1—C4—N4—C5	58.66 (19)	C11—C10—C14—O3	−39.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.81 (4)	1.87 (3)	2.6732 (19)	171 (3)
O3—H3···N2^i	0.81 (3)	1.90 (4)	2.677 (2)	161 (3)
C1—H1B···N3^ii	0.99	2.46	3.401 (2)	158
C2—H2A···N4^iii	0.99	2.86	3.791 (2)	157
C6—H6A···O2^iv	0.99	2.62	3.585 (3)	165
C6—H6B···O4^v	0.99	2.4	3.342 (3)	160

Symmetry codes: (i) −x+5/4, y−1/4, z−1/4; (ii) x, y, z−1; (iii) x+1/4, −y+5/4, z+1/4; (iv) x−1/4, −y+5/4, z+3/4; (v) −x+1, −y+1, z+1.